Lubricating compositions

ABSTRACT

A boron-containing heterocyclic compound prepared by reacting a primary amine or ammonia with an alkylene oxide or epoxide and then reacting concurrently or subsequently this reaction intermediate with a boric acid. This boron-containing heterocyclic compound may further be reacted with a metal, metaloid or other metal compound and even further contain sulfur, such as a sulfide group. 
     The boron-containing heterocyclic compound provides extreme pressure anti-wear properties when provided in a lubricating composition. The lubricating composition may also comprise anti-oxidants, copper corrosion inhibitors, and lead corrosion inhibitors. The anti-wear properties of a lubricating composition can be enhanced using the borates of the present invention in conjunction with a copper compound.

This application is a continuation-in-part of (1) U.S. patentapplication Ser. No. 525,718 filed Aug. 23, 1983, which itself is acontinuation-in-part of U.S. patent application Ser. No. 158,981, filedJune 12, 1980, and a continuation-in-part of U.S. patent applicationSer. No. 158,828, filed June 12, 1980, now U.S. Pat. No. 4,400,284, anda continuation-in-part of U.S. patent application Ser. No. 418,196,filed Sept. 15, 1982, which itself is a continuation-in-part of theaforesaid U.S. application Ser. No. 158,981 and the aforesaid U.S.application Ser. No. 158,828; and (2) U.S. patent application Ser. No.525,691, filed Aug. 23, 1983; and (3) U.S. patent application Ser. No.525,719, filed Aug. 23, 1983; and (4) U.S. patent application Ser. No.418,196, filed Sept. 15, 1982, which itself is a continuation-in-part ofU.S. patent application Ser. No. 158,981, filed June 12, 1980, and U.S.patent application Ser. No. 158,828 filed June 12, 1980, now U.S. Pat.No. 4,400,284; and (5) U.S. patent application Ser. No. 476,513, filedMar. 1, 1983; and (6) U.S. patent application Ser. No. 329,385, filedDec. 10, 1981; and (7) U.S. patent application Ser. No. 525,720, filedAug. 23, 1983, which itself is a continuation-in-part of U.S. patentapplication Ser. No. 319,073, filed Nov. 9, 1981, now U.S. Pat. No.4,410,436, and a continuation-in-part of U.S. patent application Ser.No. 329,384, filed Dec. 10, 1981, now U.S. Pat. No. 4,427,560, and acontinuation-in-part of U.S. patent application Ser. No. 329,385, filedDec. 10, 1981, and a continuation-in-part of U.S. patent applicationSer. No. 333,998, filed Dec. 23, 1981, now U.S. Pat. No. 4,412,928, anda continuation-in-part of U.S. patent application Ser. No. 434,602,filed Oct. 15, 1982, now U.S. Pat. No. 4,490,265, and acontinuation-in-part of copending U.S. patent application Ser. No.476,513, filed Mar. 1, 1983.

TECHNICAL FIELD

This invention relates to lubricating oils and more particularly toimproved lubricating oils containing additives, such as anti-wear andfriction-reducing compounds, corrosion inhibitors and oxidationinhibitors.

BACKGROUND ART

It is well recognized in the petroleum industry that boron containingcompounds are desirable additives for for lubricating oils. One suchboron containing compound is disclosed in U.S. Pat. No. 3,224,971 toKnowles et al. which relates to intracomplexed borate esters and tolubricating compositions containing said esters. The borate esters areorgano-boron compounds derived from boric acid and a bis(o-hydroxy-alkylphenyl) amine or sulfide.

Another extreme pressure lubrication composition is disclosed in U.S.Pat. No. 3,185,644 to Knowles et al., which relates to lubricatingcompositions containing amine salts of boron-containing compounds. Theamine salts are formed by reaction of a hydroxy substituted amine and atrihydrocarbyl borate. The amine-borate compounds thus formed aredescribed as useful as load carrying additives for mineral and syntheticbase lubricating oils.

Boric-acid-alkylolamine reaction products and lubricating oilscontaining the same are disclosed in U.S. Pat. No. 3,227,739 toVersteeg. These amine type products are prepared by reacting equal molarproportions of diethanolamine or dipropanolamine and a long chain, 1,2-epoxide. The intermediate reaction product thus produced is reactedwith boric acid to produce the final reaction product. These compoundsare added to lubricants to prevent rust formation.

Another boron ester composition is described in U.S. Pat. No. 3,269,853to English et al. which discloses a boron ester curing agent whichconsists of a cyclic ring structure containing boron, oxygen, nitrogen,carbon and hydrogen.

Another boron composition is disclosed in U.S. Pat. No. 3,598,855 toCyba which relates to cyclic borates of polymeric alkanolamines formedby reacting a borylating agent with a polymeric alkanolamine. Thecompounds thus formed are described as additives for a wide variety ofpetroleum products including lubricating oils.

Currently, there are phosphorus-containing additives which provideextreme pressure, anti-wear and/or friction-reducing properties toautomotive engine oils. However, with the advent of the catalyticconverter, alternative additives are needed. During combustion in anautomotive engine, any oil which leaks or seeps into the combustionchamber yields phosphorus deposits which poison the catalyst in thecatalytic converter. As a result, there is a need for automotive engineoil additives which are phosphorus-free but provide useful extremepressure, anti-wear, and/or friction-reducing properties to the oil.

Accordingly, it is one object of the invention to provide aphosphorus-free additive having such properties and which, uponcombustion, will not adversely affect the catalyst in the automotivecatalytic converter.

It is yet another object of the present invention to provideboron-containing, heterocyclic compounds or derivatives thereof whichhave extreme pressure, anti-wear and friction-reducing properties.

Yet another object of the present invention is to provide a lubricatingcomposition having extreme pressure, anti-wear and friction-reducingproperties.

A further object of the present invention is to provide a lubricatingcomposition containing extreme pressure, anti-wear, friction-reducingand corrosion prevention additives, and in addition, an anti-oxidant toprevent attack of oxidants upon metal bearings.

Other objects and advantages of the invention will be apparent from thefollowing description.

SUMMARY OF THE INVENTION

This invention resides in certain boron-containing, heterocycliccompounds and derivatives of the same having the formula: ##STR1##wherein R is an inorganic radical, or an organic radical having from 1to about 50 carbon atoms, R₁ and R₂ are the same or different organicradicals having from 1 to about 50 carbon atoms, y is an integer from 1to 4, and M is an organic or inorganic radical, and may, for example, beany metal, metalloid, or semi-metal, but preferably is either hydrogenor a transition metal having an atomic number of 21 through 30 or aGroup IVA metal of the Periodic Table. (The Periodic Table referred toherein is located in the Handbook of Chemistry and Physics, 46thEdition). If M is an organic radical, it is preferred that it be chosenfrom the group consisting of alkyl, alkenyl, alkynyl, aryl, arylalkyl,and alkylaryl radicals of between 1 and 50 carbon atoms, with methyl andcyclohexyl radicals being among the most preferred groups.

The invention additionally resides in an extreme pressure, anti-wear andfriction-reducing lubricating oil and a minor amount of aboron-containing, heterocyclic compound as above-described.

The boron-containing, heterocyclic compounds may conveniently beprepared by reacting either a saturated or unsaturated primary aminewith an organic epoxide, such as an alkyl epoxide or an aromaticepoxide, to form a reaction product. The reaction product thus formed isreacted with boric acid to form a boron-containing, heterocycliccompound. Next, the boron-containing, heterocyclic compound may bereacted with either a salt of a metal, metalloid, or semi-metal toproduce a metal derivative of the boron-containing, heterocycliccompound or with an alcohol to produce an ester-type derivative.

Alternatively, the boron-containing heterocyclic compounds may beproduced by reacting either sulfur and/or a halogen and/or a sulfurhalide with a boron-containing, heterocyclic compound containingunsaturateds in the R, R₁, R₂, and M radicals.

The above-described, boron-containing, heterocyclic compounds impartextreme pressure, anti-wear and friction-reducing properties tolubricating oils when added to said oils at use concentrations.

Another embodiment of the invention resides in a lubricating compositioncomprising a boron-containing, heterocyclic compound of the invention,and optionally any of (1) a polysulfide derivative of 2,5-dimercapto-1,3, 4-thiodiazole, (2) terephthalic acid, and (3) either abis(dithiobenzil) metal derivative, a sulfur bridged, bis(hinderedphenol) or an alkylated or dialkylated diphenyl amine or a mixturethereof.

In still another embodiment of the invention, a copper compound is usedwith a borate of the present invention in a lubricating compound. Thecopper compound enhances the anti-wear properties of such a composition.

DETAILED DESCRIPTION OF THE INVENTION

The present invention resides in extreme pressure, anti-wear andfriction-reducing lubricating oil compositions comprising a major amountof an oil of lubricating viscosity and a minor amount of aboron-containing, heterocyclic compound. Alternatively, corrosioninhibitors and anti-oxidants may be incorporated into the lubricatingcomposition.

Anti-wear, friction-reducing and extreme pressure (or "E.P.") additives,as they are commonly called, are chemicals which are added tolubricating compositions to reduce friction and reduce or preventdestructive metal-to-metal contact in the lubrication of movingsurfaces.

It has now been discovered that certain novel oil-soluble or dispersibleboron-containing, heterocyclic compounds, when added to lubricating oilsor grease, not only improve the ability of the lubricant to preventseizure of the parts being lubricated (i.e., good E.P. properties) butin addition greatly reduce the amount of friction and wear of suchmoving parts.

The boron-containing, heterocyclic compounds described herein may beincorporated in a wide variety of lubricating oils, for example, mineraloil, crude oil, synthetic oil, industrial lubricating oils, cutting oil,metal working fluids and grease. Another use for the additive of theinvention is in those fuels, e.g., certain aviation fuels and the like,wherein lubrication properties are desired. However, the most preferreduse for the lubricating additive of the invention is in automotiveengine oils. In this application, the boron-containing additives provideextreme pressure, anti-wear, and friction-reducing properties to theoil, and, upon combustion, prove innocuous to the conventional catalyticconverter in modern automobiles.

If desired, the boron-containing, heterocyclic compounds describedherein may be employed in conjunction with other additives commonly usedin petroleum products. Thus, there may be added to the oil compositionsof this invention rust and corrosion inhibitors, emulsifying agents,antioxidants or oxidation inhibitors, dyes, haze inhibitors, anti-staticagents, detergents, dispersants, viscosity index improvement agents,pour point reducing agents, and other extreme pressure and anti-wearadditives, such as the zinc dithiophosphate, triphenylphosphorothionate, etc. Soaps or other thickening agents may be added tothe lubricating oil compositions to form compositions having theconsistency of a grease. When other additives are employed, it may bedesirable, although not necessary, to prepare additive concentratescomprising concentrated solutions of the herein boron-containing,heterocyclic compounds together with said other additives whereby theseveral additives are added simultaneously. Dissolution of the additiveor additive concentrate into the oil composition may be facilitated bymixing accompanied with mild heating, but this is not absolutelyessential.

The herein-described boron-containing, heterocyclic compounds may beincorporated in the lubricating oils in any convenient way. Thus,boron-containing, heterocyclic compounds may be added directly to theoil by dissolving the desired boron derivative in the lubricating oil atthe desired level of concentration.

Normally, the boron-containing, heterocyclic compound is blended withthe lubricating oil such that its concentration is from about 0.1 toabout 15 percent by weight, preferably from about 0.5 to about 10percent by weight of the resultant oil composition. Alternatively, thecompounds may first be blended with suitable solvents to formconcentrates that may readily be dissolved in the appropriate oil at thedesired concentration. If a concentrate is prepared, it is presentlypreferred that such concentrate comprise about 75 percent by weight ofthe compound, with the balance being a solvent. Suitable solvents whichmay be used for this purpose are naphtha, light mineral oil (i.e., 150neutral to 450 neutral) and mixtures thereof. The particular solventselected should, of course, be selected so as not to adversely affectthe other desired properties of the ultimate oil composition.

The boron-containing, heterocyclic compounds of the present inventionare represented generically by the following formula (I): ##STR2## Inthe foregoing formula, R is an inorganic radical, e.g., hydrogen,chlorine, bromine, etc., or an organic radical having from about 1 toabout 50 carbon atoms, typically about 1 to 30 carbon atoms, andpreferably from about 1 to about 20 carbon atoms. Preferably, R isderived from aliphatic, alicyclic, or aromatic compounds. Mostpreferably, R is a substituted or unsubstituted hydrocarbyl group,particularly an alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkylradical having from about 1 to about 30 carbon atoms, preferably fromabout 1 to about 20 carbon atoms, especially from about 9 to about 20carbon atoms. R₁ and R₂ are the same or different organic radicalsbridging the nitrogen and oxygen atoms and have from about 1 to about 50carbon atoms and preferably from about 2 to about 30 carbon atoms, withR₁ and R₂ oftentimes containing at least 3 or at least 4 carbon atoms.R₁ and R₂ are typically derived from aliphatic, alicyclic, or aromaticcompounds and generally include at least two carbon atoms bridgedbetween the nitrogen and oxygen atoms. Usually, R₁ and R₂ are the sameor different substituted or unsubstituted hydrocarbyl or hydrocarbyloxygroups. Typical hydrocarbyl groups, which R₁ and R₂ may be, aresubstituted or unsubstituted alkylaryl, aryl, arylalkyl, alkyl, alkynyl,and alkenyl groups, with the most preferred radical bridging the oxygenand nitrogen atoms (in this and all embodiments hereinafter discussedwith the exception of the embodiment typified by formula (IV)hereinafter) being an alkylaryl group wherein an ethylene radicalbridges the oxygen and nitrogen atoms and an unsubstituted phenylradical is bonded to the carbon closest to the oxygen atom, i.e.,##STR3## Typical hydrocarbyloxy groups which may bridge the nitrogen andoxygen atoms are those discussed hereinafter with respect to formula(IV). y is an integer from 1 to 4 and M is an organic or inorganicradical, but is usually either hydrogen or a metal, typically selectedfrom the Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, andVA of the Periodic Table, as found in the "Handbook of Chemistry andPhysics," CRC Publishing Co., 46th Edition. Preferably, M is hydrogen ora transition metal having an atomic number from 21 to 30 or a Group IVAmetal of the Periodic Table or mixtures thereof, and still morepreferably copper. If M is an organic radical, it is typically of 1 to50 carbon atoms and is derived from an aliphatic, alicyclic, or aromaticcompound. Preferred radicals, when M is organic, are chosen from thegroup consisting of substituted and unsubstituted alkyl, alkynyl,alkenyl, aryl, arylalkyl, and alkylaryl groups of between 1 and 50carbon atoms, with methyl and cyclohexyl radicals being among the mostpreferred groups. Also among the most preferred groups, if M is organic,are substituted and unsubstituted phenyl groups, with substituted phenylgroups being particularly preferred. The phenyl group may be substitutedwith, for example, an acetyl group, a methyl radical, or an --O--CH.sub.3 group. One of the most preferred substituted phenyl groups is thehindered phenyl group wherein the phenyl group is substituted at the 2and 6 carbon atom of the phenyl ring with an organic group having morethan 3 carbon atoms, e.g., the 2,6-di-tert-butyl phenyl groups, such as4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl groups provide thecompound with hydrolytic stability. It has also been unexpectedly foundthat non-hindered phenyl groups, whether substituted or unsubstituted,also provide the compound with hydrolytic stability.

(It should be noted herein that the terms "alkyl," "alkenyl," and"alkynyl" include cyclic species thereof, as well as the straight andbranched chain species thereof. Also, for purposes of this invention, an"organic radical" is one which contains at least one carbon atom whereasan "inorganic radical" contains none. The term "inorganic radical," asused herein, is intended to include metals, semi-metals, and metalloids,as well as true inorganic radicals, e.g., --Cl, --Br, --I, --SO₃, and--H. The metals, semi-metals, and metalloids may be bonded ionically,covalently, or associatively.)

In one embodiment of the invention, useful when M is either hydrogen ora metal, but particularly when M is hydrogen, R is hydrogen or asubstituted or unsubstituted hydrocarbyl group and at least one of R₁and R₂, if both are aromatic, is other than an unsubstituted or alkylsubstituted ortho-alkyl phenyl bridge, with the oxygen bonded at theortho position relative to the alkyl group. Usually, if both R₁ and R₂are aromatic, at least one contains no carbon atoms or three to fivecarbon atoms of the same aromatic ring in a chain of atoms bridging (orconnecting) the oxygen atom to the nitrogen atom. Generally in thisembodiment, R contains at least 9 carbon atoms if aliphatic and at least7 carbon atoms if aromatic; further, R in this embodiment, and sometimesalso R₁ and R₂, are organic radicals other than hydroxyhydrocarbylgroups, and particularly other than alkanol groups. Further still, it ispreferred that at least one of R₁ and R₂ in this embodiment and evenmore preferably both are radicals other than an amino orhydrocarbylamino group, and it is further preferred that R₁ and R₂contain only carbon atoms bridging the nitrogen and oxygen atoms, withnone of said bridging carbon atoms being a member of an aromatic ring.

In a preferred embodiment, boron-containing, heterocyclic compounds ofthe present invention are of the following formula (II): ##STR4## Inthis formula, R₃ is hydrogen or an organic radical having from about 1to about 30 carbon atoms, preferably from about 1 to about 20 carbonatoms. Most preferably, R₃ is hydrogen or a substituted or unsubstitutedalkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radical havingfrom about 1 to about 30 carbon atoms, preferably from about 1 to about20 carbon atoms. R₄, R₅, R₆ and R₇ are the same or different and areeither an inorganic radical such as hydrogen or an organic radical, suchas substituted or unsubstituted hydrocarbyl radicals having from 1 toabout 50 carbon atoms, preferably from about 1 to 30 carbon atoms,wherein at least one (and preferably at least two) of the said R₄, R₅,R₆ or R₇ is an aryl, alkylaryl or arylalkyl radical having from about 6to about 30 carbon atoms. R₈, R₉, R₁₀ and R₁₁ are the same or differentradicals selected from hydrogen or organic radicals such as substitutedor unsubstituted hydrocarbyl groups; typically, R₈, R₉, R₁₀ and R₁₁ areeither hydrogen or an alkyl group having from about 1 to about 6 carbonatoms. y₁ is an integer from 1 to 4, and M₁ is an inorganic or organicradical, but is preferably selected from hydrogen or a metal, typicallyselected from a transition metal having an atomic number of 21 through30 or a Group IVA metal. If M₁ is an organic radical, it is typically of1 to 50 carbon atoms and is derived from an aliphatic, alicyclic, oraromatic compound. Preferred radicals, when M is organic, are chosenfrom the group consisting of substituted and unsubstituted alkyl,alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups of 1 to 50carbon atoms, with methyl and cyclohexyl radicals being among the mostpreferred. Also among the most preferred groups, if M is organic, aresubstituted and unsubstituted phenyl groups, with substituted phenylgroups being particularly preferred. The phenyl group may be substitutedwith, for example, an acetyl group, a methyl radical, or an --O--CH₃group. One of the most preferred substituted phenyl groups is thehindered phenyl group wherein the phenyl group is substituted at the 2and 6 carbon atom of the phenyl ring with an organic group having morethan 3 carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such as4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl groups provide thecompound with hydrolytic stability. It has also been unexpectedly foundthat non-hindered phenyl groups, whether substituted or unsubstituted,also provide the compound with hydrolytic stability.

In a preferred embodiment of the invention, R₄, R₇, R₈, R₉, R₁₀ and R₁₁in formula (II) are hydrogen or substituted or unsubstituted alkylgroups, with hydrogen being especially preferred for all six radicals,and R₅ and R₆ are aromatic radicals, preferably such as alkylaryl,arylalkyl, or aryl radicals, but most preferably are both unsubstitutedphenyl radicals. This embodiment of the invention, i.e., the embodimentcontaining aromatic radicals (and particularly unsubstituted phenylradicals), has the added advantage of enhanced hydrolytic stability andsolubility in lubricating oils.

The above-described, boron-containing, heterocyclic compounds areproduced by (A) reacting a primary amine or ammonia with an alkyleneoxide or epoxide or an aromatic oxide. The resulting product is thenreacted with boric acid to give the corresponding boron-containing,heterocyclic compound. Primary amines useful in preparing theheterocyclic compounds of the present invention have the chemicalformula RNH₂ wherein R is an organic or inorganic radical, preferablywhere R contains no more than 30 carbon atoms. Amines which are suitablefor use herein include saturated amines such as methylamine, ethylamine,propylamine, butylamine, octadecylamine, dodecylamine, cyclohexylamine,phenylamine, cocoamine, and unsaturated amines such as tallowamine andoleylamine and mixtures thereof. The organic radical associated withsuch amines (e.g., the methyl group of methylamine, the ethyl group ofethylamine, etc.) will ultimately be the R group side chain emanatingfrom the nitrogen atom of the heterocyclic borate of the invention.Thus, the R group side chain is determined by choice of amine, and if itis desired that R be inorganic rather than organic, then one may selectammonia to ensure that R is hydrogen, bromoamine to ensure that R isbromine, chloroamine to ensure that R is chlorine, hydroxylamine toensure that R is an OH group, etc. However, since it is preferred in allembodiments of the invention that the R group side chain be organic innature, the preferred amines for use in preparing the heterocyclicborates of the invention will be of formula RNH₂, wherein R is anorganic radical.

A wide variety of alkylene oxides or epoxides may be used to prepare theprecursor for the heterocyclic compounds herein. Typical alkylene oxidesor epoxides which are suitable for use include ethylene oxide, propyleneoxide, 1,2-epoxy-butane, cyclohexene oxide, cyclooctene oxide, andcyclododecene oxide, and mixtures thereof.

Generally, the primary amine (or ammonia) is reacted with an alkyleneoxide or epoxide, optionally in the presence of a solvent, for exampletoluene, to produce a dialkoxylated amine. The primary amine and alkeneoxide or epoxide are reacted at a molar ratio typically of about 1:2. Ifadded, the solvent is introduced in sufficient quantity to dissolve ordisperse the reactants. After the reaction proceeds to completion, thesolvent is removed from the reaction product, for example, byevaporation, distillation, etc.

Next, the dialkoxylated amine is reacted with boric acid at a typicalmolar ratio of about 1:1, optionally in the presence of a solvent, forexample, xylenes, benzene, toluene, etc., to produce the heterocycliccompound required herein. If used, the solvent will normally comprisefrom about 20 to about 50 weight percent, especially from about 30 toabout 40 weight percent of the reaction mixture. The heterocycliccompound thus produced will contain from about 0.5 to about 10 weightpercent, preferably from about 2 to about 5 weight percent of boron. Thereactions herein are typically conducted under reflux at a temperatureof from about 176° F. (80° C.) to about 392° F. (200° C.), especiallyfrom about 176° F. (80° C.) to about 300° F. (148.89° C.), atatmospheric pressure for about 1 to about 5 hours.

It is also possible to prepare a suitable heterocyclic compound hereinfrom an aromatic oxide (or aromatic epoxides). Aromatic oxides (oraromatic epoxides) suitable for use herein preferably are of thefollowing formula (III): ##STR5## wherein at least one of said R₁₂, R₁₃,R₁₄ or R₁₅ is aryl, alkylaryl or arylalkyl with the remaining R groupsbeing independently hydrogen or an organic radical having 1 to 30 carbonatoms, preferably hydrogen or an alkyl radical having 1 to 6 carbonatoms.

A wide variety of aromatic oxides may be used to prepare theepoxide/primary amine adducts needed to produce the boron compounds inthe invention. Typical aromatic oxides for use herein include styreneoxide, alpha-methylstyrene oxide, para-tertiary-butylstyrene oxide,cresyl glycidyl ether, ortho-methylstyrene oxide, 1,2-epoxybenzene, andpara-methyl styrene oxide and mixtures thereof. It should be noted that,of all the embodiments of the invention, the most highly preferred arethose produced by borating the intermediate reaction product of aprimary amine or ammonia with styrene oxide, with the resulting boroncompound having a ring structure wherein ethylene groups connect thenitrogen and oxygen atoms of the ring and unsubstituted phenyl groupsare attached to the carbon atom of said ethylene groups which are bondedto the oxygen atoms.

When an aromatic oxide is selected as a starting material, the primaryamine may be reacted with the aromatic oxide in the presence of asolvent, for example, toluene, to produce an epoxide/amine adduct. Thesolvent is added in sufficient quantity to dissolve or disperse thereactants.

Generally, the primary amine and aromatic oxide are reacted at apressure of from about atmospheric pressure to about 500 p.s.i.g. (35atmospheres) at a temperature of from 176° F. (80° C.) to 392° F. (200°C.), for 1 to 5 hours. The primary amine is preferably reacted with thearomatic oxide at a molar ratio of 1:2 to produce an epoxide/amineadduct. It may be desirable to react the primary amine with twodifferent aromatic oxides to produce a mixed epoxide/amine adduct. Inthis embodiment of the invention, one mole of the primary amine isreacted with one mole each of two different aromatic oxides to producethe desired tertiary amine. Yet another method of producing the desiredepoxide/amine adduct involves reacting one mole of anaromatic-substituted alkene oxide and one mole of an alkene oxide, forexample ethylene oxide, with a primary amine to produce an epoxide/amineadduct having an aromatic moiety and an alkyl moiety attached to thenitrogen atom.

Next, the epoxide/amine adduct is reacted with boric acid at a molarratio of about 1:1, optionally in the presence of a solvent, forexample, xylene, benzene, toluene, or the like, to produce aboron-containing, heterocyclic compound of the present invention. If asolvent is used, it will normally comprise from about 20 to about 50weight percent, preferably from about 30 to about 40 weight percent ofthe reaction mixture. The reaction is conducted under reflux at atemperature of from 176° F. (80° C.) to 392° F. (200° C.), preferablyfrom 176° F. (80° C.) to 300° F. (148.89° C.), at a pressure of fromatmospheric pressure to about 500 p.s.i.g. (35 atmospheres), for about 1to about 5 hours. The boron-containing heterocyclic compound thusproduced will contain from about 0.5 to about 10 weight percent,preferably from about 2 to about 5 weight percent of boron.

Typical boron-containing, heterocyclic compounds herein which containalkyl species in the heterocyclic ring structure are selected from thegroup consisting of methylaminodiethylate hydrogen borate,ethylaminodiethylate hydrogen borate, propylaminodiethylate hydrogenborate, butylaminodiethylate hydrogen borate, octadecylaminodiethylatehydrogen borate, dodecylaminodiethylate hydrogen borate,cyclohexylaminodiethylate hydrogen borate, phenylaminodiethylatehydrogen borate, oleylaminodiethylate hydrogen borate,cocoaminodiethylate hydrogen borate, tallowaminodiethylate hydrogenborate, dodecylamino di(-2-methylethylate) hydrogen borate, anddodecylamino di(-2-phenylethylate) hydrogen borate and mixtures thereof.

Representative boron-containing, heterocyclic compounds which containalkylaryl species on the heterocyclic ring structure include thefollowing compounds: 1-hydroxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacylooctane;1-hydroxy-4,6-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-dimethyl-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-dimethyl-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,7-dimethyl-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-para-tertiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-para-tertiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,7-para-tertiarybutyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane; and1-hydroxy-3,7 -diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane andmixtures thereof. It should be noted that the methyl, ethyl, propyl,butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco, tallow andthe like moieties may be substituted for the dodecyl moiety in the aboveheterocyclic compounds.

Metal derivatives of the boron-containing, heterocyclic compounds hereinare conveniently prepared by contacting the boron-containing,heterocyclic compound with a metal or metal compound, usually a metal insalt form. Thus, the metal acetates, propionates, etc., are suitable foruse. The preferred metal compound for use in incorporating the metal ioninto the borate of the invention is the metal acetate. Generally, theheterocyclic compounds are reacted with the metal compounds in a molarratio range of from about 1:1 to about 6:1, preferably from about 1:1 toabout 4:1, at a pressure of from about atmospheric to about 500 p.s.i.g.(35 atmospheres) and a temperature of from about 176° F. (80° C.) toabout 392° F. (200° C.). Water and, in the case where metal acetates areused, acetic acid are then distilled from the reaction mixture using awater-cooled condenser. (It should be noted that not all metal salts aredesirable for incorporating the metal ion into the boron-containing,heterocyclic compound. The metal carbonates, nitrates, chlorides, andsulfates, to name a few, are all undesirable as vehicles for impartingmetal ions into the boron-containing, heterocyclic compound. These metalsalts experience solubility problems and separation problems, and, inaddition, undesirable ions frequently contaminate the boron-containing,heterocyclic compound.) Generally, the boron-containing, heterocycliccompounds are reacted with the metal compounds herein in a molar ratiorange of from about 1:1 to about 6:1, especially from about 1:1 to about4:1.

Desirable metals are usually selected from transition metals having anatomic number of 21 through 30 or Group IVA metals of the PeriodicTable. Transition metals which are suitable for use are selected fromscandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel,copper and zinc and mixtures thereof. Suitable Group IVA metals includelead and tin and mixtures thereof. Other metals (or metalloids orsemi-metals) may also be selected, such as gallium, bismuth, andantimony. Normally, the metal will comprise from about 1 to about 17weight percent, preferably from about 5 to about 9 weight percent of theboron-containing, heterocyclic compound.

Representative metallic derivatives of the above compositions includethe following compounds: copperdi(1-oxy-3-,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacylooctane;copperdi-(1-oxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,6-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copper di-(1-oxy-3,7-dimethyl-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,6-dimethyl-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copperdi-(1-oxy-4,7-dimethyl-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copper di-(1-oxy-3,7-paratertiary-butyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copper di-(1-oxy-4,6 paratertiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copper di-(1-oxy-4,7-paratertiary-butyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);copper di-(1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane); and copperdi-(1-oxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane).Other metals may be incorporated into the above compounds, i.e.,substituted for the copper, for example, scandium, titanium, chromium,manganese, iron, cobalt, nickel, zinc, lead and tin and mixturesthereof. In addition, methyl, ethyl, propyl, butyl, cyclohexyl,octadecyl, phenyl, steryl, oleyl, coco, tallow and the like moieties maybe substituted for the dodecyl moiety in the above-describedheterocyclic compounds.

If it is desired that M in formula (I) hereinbefore, and also for thecorresponding M radical of any of the borate of the invention formulasherein, be organic, then one may employ the following procedure: theborate of the invention is reacted under conditions as set forthhereinbefore with respect to preparing metal derivatives, but instead ofusing a metal salt, an alcohol of choice is employed and no water isadded to the reaction. For example, if a methyl radical is desired forM, then methanol is employed; if a cyclohexyl radical, thencyclohexanol; and if an unsubstituted phenyl radical, then phenol.Optionally, a solvent such as toluene or xylene is also used. After thereaction is complete, water is removed by distillation, and the desiredborate of the invention is obtained.

Another procedure, preferred especially for preparing borates of theinvention with M as a substituted phenyl group, involves reacting thealcohol of choice, e.g., 2,6-tert-butyl phenol, optionally in thepresence of a solvent such as toluene or xylene, with boric acid in thepresence of an acid catalyst, e.g., para-toluenesulfonic acid, or otherorganic soluble acids (e.g., acetic) or an ion exchange resin catalyst,Amberlyst 15, which is strongly acidic. The reaction may be accomplishedby refluxing, which removes two moles of water for every mole of boricacid which reacts with the phenol compound. The resulting product, aboric acid:phenol adduct is in turn reacted with an amine:epoxideadduct, under conditions hereinbefore specified for reacting boric acidwith an amine:epoxide adduct, and after water is removed bydistillation, the final desired product is recovered.

Another species of the heterocyclic compounds herein are thebis(hydrocarbyloxy methylated) boron-containing, heterocyclic compounds.These compounds are of the following formula (IV): ##STR6## where R₁₆ isan inorganic radical or an organic radical having from 1 to about 50carbon atoms, R₁₇ and R₁₈ are the same or different organic radicalshaving from 1 to about 50 carbon atoms, y₂ is an integer from 1 to 4,and M₂ is an organic or inorganic radical but preferably is hydrogen ora metal, typically selected from a transition metal having an atomicnumber of 21 through 30 or a Group IVA metal as disclosed in thePeriodic Table located in the Handbook of Chemistry and Physics, 46thEdition. If M₂ is an organic radical, it is preferred that it be chosenfrom the group consisting of substituted or unsubstituted alkyl,alkenyl, alkynyl, aryl, arylalkyl, and alkylaryl radicals having from 1to 50 carbon atoms, with methyl and cyclohexyl radicals being among themost preferred groups. Also among the most preferred groups, if M isorganic, are substituted and unsubstituted phenyl groups, withsubstituted phenyl groups being particularly preferred. The phenyl groupmay be substituted with, for example, an acetyl group, a methyl radical,or an --O--CH₃ group. One of the most preferred substituted phenylgroups is the hindered phenyl group wherein the phenyl group issubstituted at the 2 and 6 carbon atom of the phenyl ring with anorganic group having more than 3 carbon atoms, e.g., 2,6-di-tert-butylphenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl. Hinderedphenyl groups provide the compound with hydrolytic stability. It hasalso been unexpectedly found that non-hindered phenyl groups, whethersubstituted or unsubstituted, also provide the compound with hydrolyticstability.

When R₁₆, R₁₇ and R₁₈ are organic radicals, usually at least 65 percent,more usually at least 75 percent, and most usually at least 90 percentof the atoms composing said radicals will be carbon and hydrogen atoms.Preferably, R₁₆ is hydrogen or a substituted or unsubstituted alkyl,alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical having from 1 toabout 30 carbon atoms, and more preferably, from 1 to about 24 carbonatoms. On the other hand, R₁₇ and R₁₈ are preferably the same ordifferent radicals selected from a substituted or unsubstituted alkyl,alkenyl, alkynyl, aryl, alkylaryl and arylalkyl radicals having from 1to about 50 carbon atoms, and more preferably from 1 to about 30 carbonatoms, more preferably still from 1 to about 20 carbon atoms, and mostpreferably from 1 to about 10 carbon atoms.

In preparing the bis(hydrocarbyloxy methylated) boron-containing,heterocyclic compounds, a primary amine or ammonia (but preferably aprimary amine) is reacted with an alkyl, aryl, alkylaryl or arylalkylglycidyl ether to produce a bis(hydrocarbyloxy methylated) primaryamine. Glycidyl ethers suitable for use herein preferably are of thefollowing formula (V): ##STR7## where R₁₉ is an organic radical having 1to 50 carbon atoms with said organic radical in a preferred modecomprising at least 75 percent, preferably 90 percent of carbon andhydrogen atoms. Preferably, R₁₉ is a substituted or unsubstituted alkyl,aryl, alkylaryl or arylalkyl radical having from 1 to about 50 carbonatoms, preferably from 1 to about 30 carbon atoms, more preferably stillfrom 1 to about 20 carbon atoms, and most preferably from 1 to about 10carbon atoms.

A wide variety of glycidyl ethers may be used to prepare the oxylatedprimary amines needed to produce the heterocyclic compounds herein.Typical glycidyl ethers for use herein include methyl glycidyl ether,ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether,phenyl glycidyl ether, cresyl glycidyl ether, phenyl methyl glycidylether, ethyl phenyl glycidyl ether and phenyl ethyl glycidyl ether andmixtures thereof.

The primary amine may be reacted with the glycidyl ether in the presenceof a solvent, for example, toluene to produce a dioxygenated amine. Thesolvent is added in sufficient quantity to dissolve or disperse thereactants.

Generally, the primary amine and glycidyl ether are reacted at apressure of from about atmospheric pressure to about 500 p.s.i.g. (35atmospheres) at a temperature of from 176° F. (80° C.) to 392° F. (200°C.) for 1 to 30 hours. The primary amine is preferably reacted with theglycidyl ether at a molar ratio of 1:2 to produce the bis(hydrocarbyloxymethylated) amine. It may be desirable to react the primary amine withtwo different glycidyl ethers to produce a mixed hydrocarbyloxymethylated amine. In this embodiment of the invention, one mole of theprimary amine is reacted with one mole each of two different glycidylethers to produce the desired mixed hydrocarbyloxy methylated amine. Yetanother method of producing the desired amine involves reacting one moleof an aromatic glycidyl ether and one mole of an alkyl glycidyl etherwith a primary amine to produce an amine having an alkylaryl moiety andan alkyl moiety attached to the nitrogen atom of the amine.

Next, the bis(hydrocarbyloxy methylated) amine or mixed hydrocarbyloxymethylated amine is reacted with boric acid at a molar ratio of fromabout 1:1, optionally in the presence of a solvent, for example, xylene,benzene, toluene, or the like, to produce a bis(hydrocarbyloxymethylated) boron-containing, heterocyclic compound of the presentinvention. Normally, the solvent, if used, will comprise from about 20to about 50 weight percent, preferably from about 30 to 40 weightpercent of the reaction mixture. The reaction is conducted under refluxat a temperature of from 176° F. (80° C.) to 392° F. (200° C.), at apressure of from atmospheric pressure to about 500 p.s.i.g. (35atmospheres) for about 1 to about 30 hours. The compound thus producedwill contain from about 0.5 to about 10 weight percent, preferably fromabout 2 to about 5 weight percent of boron.

In a preferred mode the primary amine and glycidyl ether are firstreacted together and the intermediate reaction product thus produced is,next, reacted with boric acid.

An alternative method of producing the bis(hydrocarbyloxy methylated)boron-containing, heterocyclic compounds herein involves reacting theprimary amine, glycidyl ether and boric acid in a one-step process.

Representative bis(hydrocarbyloxy methylated), boron-containing,heterocyclic compounds produced in accordance with the procedure hereininclude the following compounds:1-hydroxy-3,7-di-(methoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-di-(methoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-di-(ethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-di-(propoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-di-(butoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-di-(methylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-di-(methylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-3,7-di-(ethylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;1-hydroxy-4,6-di-(phenylmethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;and1-hydroxy-3,7-di-(phenylethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacylooctaneand mixtures thereof. It should be noted that the methyl, ethyl, propyl,butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco and tallowmoieties may be substituted for the dodecyl moiety in the aboveheterocyclic compounds. This embodiment of the invention has the addedadvantage of enhanced extreme pressure properties and a more pleasantodor.

Metal derivatives of the bis(hydrocarbyloxy methylated),boron-containing, heterocyclic compounds, herein are convenientlyprepared by contacting the compound with a metal, usually in salt form.Thus, the metal acetates, proprionates, etc., are suitable for use. Thepreferred metal compound for use in incorporating the metal ion into thebis(hydrocarbyloxy methylated) boron-containing, heterocyclic compoundis the metal acetate. Generally, these compounds are reacted with themetal compounds in a molar ratio range of from about 1:1 to about 6:1,preferably from about 1:1 to about 4:1, at a pressure of from aboutatmospheric to about 500 p.s.i.g. (35 atmospheres) and a temperature offrom about 176° F. (80° C.) to about 392° F. (200° C.). Water and, inthe case where metal acetates are used, acetic acid are distilled fromthe reaction mixture using a water-cooled condenser.

Representative of the metal compounds are: copperdi[-1-oxy-2,7-di-(methoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-4,6-di(methoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-3,7-di-(ethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclo-octane];copperdi-[1-oxy-3,7-di-(propoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-4,6-di-(butoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-3,7-di-(methylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-4,6-di-(methylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-3,7-di(ethylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];copperdi-[1-oxy-4,6-di(phenylmethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane];and copperdi-[1-oxy-3,7-di-(phenyl-ethoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]andmixtures thereof. Other metals may be incorporated into the abovecompounds, i.e., substituted for the copper, for example, scandium,titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc,lead and tin and mixtures thereof. Semi-metals and metalloids may alsobe incorporated into such compounds. In addition, methyl, ethyl, propyl,butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco and tallowmoieties may be substituted for the dodecyl moiety in theabove-described compounds.

It should be noted that the foregoing bis(hydrocarbyl methylated)boron-containing compounds of formula (IV) have been found to be solublein 450 neutral oil, at least when prepared with tallowamine orcocoamine. However, the higher cost of preparing such compounds,particularly in comparison to compounds of formula (II) structureprepared with styrene oxide, makes the latter, i.e., the formula (II)compounds prepared from styrene oxide, a more preferred additive forautomotive lubricating engines.

Also suitable herein are sulfohalogenated, boron-containing,heterocyclic compounds of the following formula (VI): ##STR8## whereinR₃₄ and R₃₆ may be the same or different organic or inorganic radicalsbut more typically R₃₄ and R₃₆ are well as R₃₅ and R₃₇ are the same ordifferent organic radicals having from about 1 to about 30 carbon atoms,R₃₈, R₃₉, R₄₀ and R₄₁ are the same or different organic radicals havingfrom about 1 to about 50 carbon atoms, n₂ is an integer from 1 to 4,preferably 1 or 2, X and X₁ are halogens independently selected from thegroup consisting of chlorine, fluorine, bromine and iodine and mixturesthereof, with chlorine being especially preferred. The radicals R₃₄,R₃₅, R₃₆ and R₃₇ are typically selected from the same or different,substituted or unsubstituted hydrocarbyl groups, such as, substituted orunsubstituted aliphatic and aromatic groups, particularly the alkyl,alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radicals having fromabout 1 to about 30 carbon atoms, preferably from about 1 to about 20carbon atoms. The organic radicals R₃₈, R₃₉, R₄₀ and R₄₁ are typicallyselected from the same or different, substituted or unsubstitutedhydrocarbyl groups, such as, substituted or unsubstituted aliphatic andaromatic groups, particularly the alkyl, alkenyl, alkynyl, aryl,alkylaryl, or arylalkyl radicals having from about 1 to about 50 carbonatoms, preferably from about 1 to about 30 carbon atoms. Preferably R₃₈,R₃₉, R₄₀ and R₄₁ are alkylaryl or arylalkyl having from about 8 to about30 carbon atoms. More preferably, R₃₈, R₃₉, R₄₀, and R₄₁ are alkylarylgroups and, most preferably, are alkylaryl groups wherein ethyleneradicals connect the nitrogen and oxygen atoms and unsubstituted phenylradicals are bonded to the carbon atoms of the ethylene radicals bondedto the oxygen atoms. Y₇ and Y₈ are the same or different integers from 1to 4, and M₇ and M₈ may be an organic or inorganic group, but preferablyare either hydrogen or a metal with the metal typically a transitionmetal having an atomic number from 21 to 30 or a Group IVA metal of thePeriodic Table or mixtures thereof. If M₇ or M₈ is an organic radical,it is preferred that it be chosen from the group consisting ofsubstituted and unsubstituted alkyl, alkenyl, alkynyl, aryl, arylalkyl,and alkylaryl radicals of between 1 and 50 carbon atoms, with methyl andcyclohexyl radicals being among the most preferred groups. Also amongthe most preferred groups, if M is organic, are substituted andunsubstituted phenyl groups, with substituted phenyl groups beingparticularly preferred. The phenyl group may be substituted with, forexample, an acetyl group, a methyl radical, or an --O--CH₃ group. One ofthe most preferred substituted phenyl groups is the hindered phenylgroup wherein the phenyl group is substituted at the 2 and 6 carbon atomof the phenyl ring with an organic group having more than 3 carbonatoms, e.g., 2,6-di-tert-butyl phenyl groups, such as4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl groups provide thecompound with hydrolytic stability. It has also been unexpectedly foundthat non-hindered phenyl groups, whether substituted or unsubstituted,also provide the compound with hydrolytic stability. M₇ and M₈ may bethe same physical atom or species, e.g., the two borated radicals may beattached to the same metal atom or together may be one organic radical.

Halogenated, boron-containing, heterocyclic compounds useful in thepresent invention are of the following formula (VII): ##STR9## whereinR₄₂ may be an inorganic radical but more typically R₄₂ and R₄₃ are thesame or different organic radicals having from about 1 to about 30carbon atoms, R₄₄ and R₄₅ are the same or different organic radicalshaving from about 1 to about 50 carbon atoms, X₂ and X₃ are halogensselected from the group consisting of chlorine, fluorine, bromine andiodine and mixtures thereof, with chlorine and bromine being especiallypreferred. The radicals R₄₂ and R₄₃ are typically selected from the sameor different, substituted or unsubstituted hydrocarbyl groups, such assubstituted or unsubstituted aliphatic and aromatic groups, particularlythe alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radicalshaving from about 1 to about 30 carbon atoms, preferably from about 1 toabout 20 carbon atoms. The organic radicals R₄₄ and R₄₅ are typicallyselected from the same or different, substituted or unsubstitutedhydrocarbyl groups, such as, substituted or unsubstituted aliphatic andaromatic groups, particularly the alkyl, aryl, alkylaryl or arylalkylradicals having from about 1 to about 50 carbon atoms, preferably fromabout 1 to about 30 carbon atoms. Preferably, R₄₄ and R₄₅ are alkylarylor arylalkyl having from about 8 to about 30 carbon atoms. Morepreferably, R₄₄ and R₄₅ are alkylaryl groups and, most preferably, arealkylaryl groups wherein ethylene radicals connect the nitrogen andoxygen atoms and unsubstituted phenyl radicals are bonded to the carbonatoms of the ethylene radicals bonded to the oxygen atoms. Y.sub. 9 isan integer from 1 to 4, and M₉ may be an organic or inorganic group, butpreferably is either hydrogen or a transition metal having an atomicnumber between 21 and 30 or a Group IVA metal of the Periodic Table andmixtures thereof. If M₉ is an organic radical, it is preferred that itbe chosen from the group consisting of substituted and unsubstitutedalkyl, alkenyl, alkynyl, aryl, arylalkyl, and alkylaryl radicals ofbetween 1 and 50 carbon atoms, with methyl and cyclohexyl radical beingamong the most preferred groups. Also among the most preferred groups,if M is organic, are substituted and unsubstituted phenyl groups, withsubstituted phenyl groups being particularly preferred. The phenyl groupmay be substituted with, for example, an acetyl group, a methyl radical,or an --O--CH₃ group. One of the most preferred substituted phenylgroups is the hindered phenyl group wherein the phenyl group issubstituted at the 2 and 6 carbon atom of the phenyl ring with anorganic group having more than 3 carbon atoms, e.g., 2,6-di-tert-butylphenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl. Hinderedphenyl groups provide the compound with hydrolytic stability. It hasalso been unexpectedly found that non-hindered phenyl groups, whethersubstituted or unsubstituted, also provide the compound with hydrolyticstability.

Halogenated boron-containing, heterocyclic compounds typically include1-hydroxy-3,7-diphenyl-5-(9-10-dichlorooctadecyl)-1-bora-2,8-dioxa-5-aza-cyclooctane;1-hydroxy-3,7-diphenyl-5-(9-10-dichlorostearyl)-1-bora-2,8-dioxa-5-aza-cyclooctane;and1-hydroxy-3,7-diphenyl-5-(dichlorotallow)-1-bora-2,8-dioxa-5-aza-cyclooctaneand mixtures thereof. Other halogens which may be substituted for thechlorine above include fluorine, bromine and iodine and mixturesthereof.

Sulfurized forms of the borate of the invention are of the followingformula (VIII): ##STR10## wherein R₅₄ is an inorganic or organicradical, R₅₅ and R₅₆ are the same or different organic radicals, and M₁₀is an organic or inorganic radical, with Y₁₀ being the valence of M₁₀,and preferably an integer from 1 to 4, further provided that at leastone of R₅₄, R₅₅, R₅₆, and M₁₀ contains sulfur. Thus, for example, one ormore of R₅₄, R₅₅, R₅₆, and M₁₀ may contain a "sulfide group," which isherein defined as sulfur bonded (1) as an end group as represented by athio-group (--SH), (2) as part of the compound backbone (--CH_(x)--S--CH_(x) --), (3) as a pendant from the compound as represented by anepisulfide group ##STR11## or (4) one or more sulfide or polysulfidebridges (--S-- or --S.sub.(n) --, wherein --S.sub.(n) -- represents twoor more sulfur atoms bonded in series) connected to an organic radical,including another organic radical in formula (VIII) and an organicradical in a second borate of the invention of formula (VIII) structureor any of the borates of the invention previously illustrated byformula.

The preferred sulfurized borate of the invention contains a sulfide orpolysulfide bridge connecting two borates of the invention, with themost preferred location of the bridge being between the two side Rgroups, i.e., as shown in the following formula (IX): ##STR12## whereinall of the R groups are the same or different organic radicals and M₁₁and M₁₂ are the same or different organic or inorganic radicals and(S)n1 represents one or more sulfide or polysulfide bridges connectingR₅₇ and R₆₀.

As shown in formula (IX), one or more sulfur bridges exist between twoborates of the invention. However, it is further contemplated in theinvention that the sulfurized borate of the invention may have three ormore borates of the invention, each of formula (VIII) structure whereinthe R side groups (shown in formula (VIII) as R₅₄) and the M radicals ofthe borates of the invention may be the same or different inorganic ororganic radicals and the R groups bridging the oxygen and nitrogen atoms(shown in formula (VIII) as R₅₅ and R₅₆) are the same or differentorganic radicals. It is most highly preferred that all sulfur bridges inthe borate of the invention connect the R group side chains (R₅₄ informula (VIII) and R₅₇ and R₆₀ in formula (IX)) emanating from thenitrogen atom of each borate of the invention, in which case the R groupside chains would all be organic radicals. However, it is alsocontemplated in alternative embodiments that the sulfur bridge couldconnect elsewhere, e.g., from the R group side chain to M, from one Rgroup connecting an oxygen and nitrogen atom to another, etc.

In formulas (VIII) and (IX), R₅₄, R₅₇, and R₆₀ are preferably organicradicals, usually having from 1 to 50 carbon atoms, and may, forexample, be a substituted or unsubstituted hydrocarbyl group,particularly an alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkylradical having from 1 to 30 carbon atoms, often from about 9 to 20carbon atoms. R₅₅, R₅₆, R₅₈, R₅₉, R₆₁, and R₆₂ are generally organicradicals of 1 to 50 carbon atoms, and may, for example, be a substitutedor unsubstituted hydrocarbyloxy group, e.g., the structure bridging thenitrogen and oxygen atom in formula (IV), or a hydrocarbyl group such asan alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical.Preferably, R₅₅, R₅₆, R₅₈, R₅₉, R₆₁, and R₆₂ are alkylaryl groupswherein ethylene radicals connect the nitrogen and oxygen atoms andunsubstituted phenyl radicals are bonded to the carbon atoms of theethylene radicals bonded to the oxygen atom.

M₁₀, M₁₁, and M₁₂ are typically inorganic radicals such as hydrogen or ametal having an atomic number from 21 to 30, or a Group IVA metal. Othermetals (or metalloids or semi-metals) may also be selected, such asgallium, bismuth, and antimony. M₁₀, M₁₁, and M₁₂ may also be organicradicals, preferably chosen from substituted or unsubstituted alkyl,alkenyl, alkynyl, aryl, arylalkyl, and alkylaryl radicals with methyland cyclohexyl radicals being among the most preferred. Also among themost preferred groups, if M is organic, are substituted andunsubstituted phenyl groups, with substituted phenyl groups beingparticularly preferred. The phenyl group may be substituted with, forexample, an acetyl group, a methyl radical, or an --O--CH₃ group. One ofthe most preferred substituted phenyl groups is the hindered phenylgroup wherein the phenyl group is substituted at the 2 and 6 carbon atomof the phenyl ring with an organic group having more than 3 carbonatoms, e.g., 2,6-di-tert-butyl phenyl groups, such as4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl groups provide thecompound with hydrolytic stability. It has also been unexpectedly foundthat non-hindered phenyl groups, whether substituted or unsubstituted,also provide the compound with hydrolytic stability. Also, M₁₁ and M₁₂may be the same physical atom or species, e.g., the two borate radicalsmay be attached or bonded to the same metal atom or together may be oneorganic radical.

One of the advantages of the sulfurized form of the borates of theinvention is that of increased oxidation stability, as well assubstantially enhanced extreme pressure properties. Generally, thesulfurized compounds exhibit the same or superior extreme pressureproperties when used at weight percent concentrations substantially lessthan other heterocyclic, boron-containing compounds disclosed herein.

The sulfurized, halogenated or sulfohalogenated compounds herein areproduced in accordance with the procedure described before for producingthe boron-containing, heterocyclic compounds with the added stipulationthat the primary amine used to form the heterocyclic compound isunsaturated. Elemental sulfur is reacted with the heterocyclic compoundin toluene, xylene, or the like to produce a sulfurized compound. Thesulfohalogenated form of the compound may be produced by substituting asulfur halide for the elemental sulfur above, for example, a sulfurchloride such as sulfur monochloride, sulfur dichloride, etc. Thehalogenated form of the heterocyclic compound is produced bysubstituting a halogen for the sulfur above.

The sulfurized compounds of the invention are preferably prepared byreacting one mole of sulfur with one equivalent of unsaturateds in the Rside group of the boron heterocyclic compound or its metal derivative.For example, if1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane is thechosen boron compound to be sulfurized, then 1 mole of sulfur is reactedwith about 2.5 moles of the boron compound (because the boron compoundcontains about 0.40 equivalents of unsaturateds in the R group sidechain). The reaction is conducted in the presence of a solvent such astoluene or xylene, using at least 3 moles of solvent for every mole ofboron compound reacted. The reaction is conducted at elevatedtemperature with refluxing, with the time and temperature of reactionbeing dependent to a great extent upon the solvent chosen. If toluene,sulfurization is usually achieved in four hours at 110° C. underatmospheric pressure conditions; if xylene, then sulfurization is morerapid, occurring in 1 hour of refluxing at 137° to 140° C. underatmospheric pressure conditions. To prevent oxidation of the sulfurduring said reactions, an inert gas blanket, such as nitrogen or argon,may be employed.

In an alternative embodiment of the invention, the elemental sulfur isfirst reacted with the unsaturated primary amine followed by subsequentreaction with the desired epoxide, which is in turn followed by reactionwith boric acid. Alternatively still, an unsaturated amine:epoxideadduct may be produced first, followed by reaction with the elementalsulfur, which is in turn followed by reaction with boric acid. Reactionconditions for these embodiments typically are commensurate with thosespecified above for sulfurization reactions, reactions with boric acid,and reactions between amines and epoxides.

As stated above, the sulfurized versions of the borates of the inventiontypically form one or more sulfur bridges between R side groupsemanating from the nitrogen atom. Such sulfur bridges, which may containone sulfur atom or several in series, typically bond to carbon atomsimmediately adjacent to a phenyl ring or alkenyl or alkynylunsaturation. In other words, the sulfur bridge connects one R sidegroup of a first borate of the invention with that of a second atlocations formerly occupied by benzylic hydrogen (in the case of phenylunsaturation) or an allylic hydrogen (in the case of alkenyl or alkynylunsaturation). Thus, it will be understood that, by "unsaturateds" inthe R side group, it is meant in the present specification and claimsthe number of allylic and benzylic hydrogens available in said R sidegroup for substitution by a sulfur atom. And since the R side grouporiginates in the primary amine, it will be understood that"unsaturated" in the term "unsaturated primary amine" refers to thenumber of allylic and benzylic hydrogens available in the R group of theamine (of formula RNH₂) for substitution by a sulfur atom.

(Of course, it will also be understood that, if the R groups connectingthe nitrogen and oxygen atoms contain significant allylic and benzylichydrogens, some bonding of sulfur atoms at such locations may alsooccur. But in the preferred embodiment, wherein styrene oxide is theepoxide chosen for reaction with the amine, and particularly when thephenyl groups of said styrene oxide ultimately are attached to thecarbon atoms of the heterocyclic ring nearest the oxygen atoms, sulfursubstitution is minimal, being impeded structurally by the ring itselfand the influence of the oxygen atom.)

If desired, the sulfurization of the boron compound may be hastened byuse of a vulcanization catalyst. The presently preferred catalyst iszinc bis(dibutylthiocarbamate), which is employed in the reactionmixture in a ratio to the boron compound of 0.01 to 0.50 moles for eachmole of the boron compound.

The sulfohalogen compounds of the invention are prepared in a similarmanner to the sulfurized versions, with the exception that no solvent isemployed and, instead of sulfur as a reactant, a compound such as asulfur monochloride (S₂ Cl₂) is employed. The molar ratio of sulfurmonochloride to boron compound is preferably the same as that for thesulfur to boron compound ratio employed in preparing the sulfurizedspecies.

The halogenated species of the invention is typically prepared byintroducing the boron compound to be halogenated, said boron compoundcontaining an unsaturated R side group emanating from the nitrogen atom,into a 450 neutral oil or into a chlorinated hydrocarbon, e.g., carbontetrachloride, followed by bubbling of chlorine or fluorine into themixture at room temperature (25° C.). Generally, the bubbling takesplace for about 15 minutes, but longer times are also suitable. Ifbromine is the desired halogen, it is added to the mixture in liquidform, in sufficient amount to saturate a portion of or all theunsaturated sites of the R side group. Bromination of the boron compoundcan take place in as little as 10 minutes at 120° C. at atmosphericpressure. If iodine is the desired halogen, the procedure is modified byadding the iodine in sufficient quantity to saturate the unsaturatedsites.

Sulfohalogenated, boron-containing, heterocyclic compounds include10,10'-dithiodi[9-chloro-1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl)-octadecane];dithiodi[1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl)-chlorotallow];anddithiodi[1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl)chlorosoya]andmixtures thereof. It should be noted that fluorine, bromine and iodinemay be substituted for the chlorine above.

It will be noted in the foregoing descriptions related to thepreparation of boron heterocyclic compounds of the invention that suchdescriptions relate to preparing the compounds with solvents presentduring both reactions, i.e., the reaction of a primary amine with anoxygen-containing organic compound followed by the reaction of theresulting intermediate product with boric acid, which yields the boratedcompound of the invention. However, the preferred embodiment of theinvention as presently contemplated is that the borated compound of theinvention be produced without any solvent being employed during thesetwo reactions. (It is, however, preferred that, when preparing thesulfurized borated compounds previously described, the sulfurizing stepusing elemental sulfur be carried out in the presence of a solvent,e.g., toluene.) The reason that the absence of solvent is preferred isthat it has been discovered that a more complete reaction to the desiredborated product is accomplished when no solvent is employed. Thepresence of solvent tends to yield a mix of undesired and desiredborates of the invention whereas the absence of solvent tends toselectively yield the desired borate of the invention.

The borates of the invention have, as stated previously, excellentextreme pressure, anti-wear, and friction-reducing properties. However,they have also been found to increase the corrosiveness of automotivelubricating engine oils, with the degree of corrosiveness depending onthe purity of the borate of the invention employed, the amount employed,and the particular borate of the invention chosen. Some borates of theinvention herein are less corrosive than others; for example, a borateof the invention of formula (I) structure hereinbefore, wherein R₁ andR₂ are ethylene groups, is more corrosive than the borate of theinvention of formula (II) structure wherein R₄, R₇, R₈, R₉, R₁₀, and R₁₁are hydrogen and R₅ and R₆ are both unsubstituted phenyl radicals. Onthe other hand, some of the sulfurized borate of the invention compoundsdescribed hereinbefore are significantly more corrosive than either ofthe aforementioned formulae (I) and (II) compounds, but thisdisadvantage is compensated for by the fact that only about one-half asmuch of the sulfurized compounds is needed to provide similar anti-wear,friction-reducing, and extreme pressure properties as said formulae (I)and (II) compounds.

In any event, if it is desired to lessen the corrosiveness of theborates of the invention, the lubricating oils into which they are addedmay be further provided with one or more corrosion inhibitors. Suchcorrosion inhibitors should impart lead and/or coppercorrosion-inhibiting properties, and this because the bearings inautomotive engines typically contain lead and/or copper.

In one embodiment of the present invention, copper corrosion in enginebearings is inhibited by adding to the lubrication composition acorrosion inhibiting amount, normally from 0.001 to about 5 weightpercent, preferably from 0.005 to about 2.5 weight percent of ahydrocarbon polysulfide derivative of 2,5-dimercapto-1,3,4-thiadiazolehaving the formula (X): ##STR13## wherein R₄₆ and R₄₇ are the same ordifferent moieties selected from hydrogen or straight or branched chainalkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicalshaving from 2 to about 30 carbon atoms, and w and z are integers from 1to 8. It should be noted that R₄₆ and R₄₇ cannot both be hydrogenbecause the compound would be rendered insoluble in lubricating oils.Thus, when R₄₆ is hydrogen, R₄₇ must be selected from one of the othermoieties described above, and vice versa.

Suitable among such compounds are polysulfides of1,3,4-thiadiazole-2,5-bis(alkyl, di, tri or tetra sulfide) containingfrom 2 to about 30 carbon atoms. Desirable polysulfides include1,3,4-thiadiazole-2,5-bis(octyldisulfide);1,3,4-thiadiazole-2,5-bis(octyltrisulfide); 1,3,4-thiadiazole-2,5-bis(octyltetrasulfide); 1,3,4-thiadiazole-2,5-bis(dodecyldisulfide);1,3,4-thiadiazole-2,5-bis(dodecyltrisulfide);1,3,4-thiadiazole-2,5-bis(dodecyltetrasulfide);2-lauryldithio-5-thioalpha- methyl-styryl-1,3,4-thiadiazole;2-lauryltrithio-5-thio- alpha-methyl-styryl-1,3,4-thiadiazole;2-mercapto-5-octyl- dithio-1,3,4-thiadiazole and2-mercapto-5-dodecyldithio-1,3,4-thiadiazole and mixtures thereof.

A small amount of terephthalic acid is effective as a lead corrosioninhibitor herein. The terephthalic acid may be prepared in accordancewith conventional techniques and apparatus. Generally, the terephthalicacid is incorporated into lubricating oils at a concentration of fromabout 0.001 to about 1 weight percent, especially from about 0.005 toabout 0.05 weight percent.

An oxidation inhibitor may also be employed in conjunction with thedesired boron heterocyclic compound or in conjunction with the boronheterocyclic compound and corrosion inhibitors. Oxidation inhibitors aretypically added to lubricating oils to prevent oxidative deteriorationof organic materials. Any oxidation inhibitor known in the art may beemployed, with suitable oxidation inhibitors being selected from thegroup consisting of bis(dithiobenzil) metal derivatives; sulfur bridged,bis(hindered phenols); and alkyl or diakyl, diphenylamines,dithiocarbamates and mixtures thereof. These compounds effectively limitor prevent the attack of oxidants on copper/lead metal. In addition,these compounds also help to control oil oxidation as manifested byreduced sludge and varnish formation, and by reduced oil thickening.

The bis(dithiobenzil) metal derivatives herein preferably have theformula (XI): ##STR14## wherein M₁₀ is a first row transition metal andt is an integer from 1 to 4. Suitable transition metals includevanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,preferably iron, cobalt and nickel.

The bis(dithiobenzil) metal derivatives may be prepared, for example, byreacting benzoin with a phosphorus sulfide in the presence of dioxane atelevated temperature to produce the thiophosphoric ester ofdithiobenzoin. The desired divalent metal, for example, metallic halide,is reacted with the above-described thiophosphoric ester ofdithiobenzoin to produce the bis(dithiobenzil) metal derivative.

It should be noted that the bis(dithiobenzil) metal derivatives hereindo not readily dissolve in lubricant compositions. However, when thebis(dithiobenzil) metal derivatives are mixed with the boron-containing,heterocyclic compounds herein, especially dodecylaminodi(phenylethylate)hydrogen borate, the mixture goes into solution in lubricantcompositions such as motor oils.

The sulfur bridged, bis hindered phenols herein preferably have theformula (XII): ##STR15## wherein R₄₈ and R₄₉ are selected from the sameor different alkyl groups having from 1 to 6 carbon atoms.

Sulfur bridged, bis(hindered phenols) which are suitable for use asanti-oxidants include thiodiethyl bis(3,5-dimethyl-4-hydroxy)hydrocinnamate; thiodiethylbis(3,5-diethyl-4-hydroxy) hydrocinnamate;thiodiethyl bis(3,5-dipropyl-4-hydroxy) hydrocinnamate; thiodiethylbis(3,5-dibutyl-4-hydroxy) hydrocinnamate; thiodiethylbis(3,5-dipentyl-4-hydroxy) hydrocinnamate and thiodiethylbis(3,5-dihexyl-4-hydroxy) hydrocinnamate and mixtures thereof.

One unexpected result in the present invention is that, when asulfur-bridged, bis hindered phenol is employed as an oxidationinhibitor in the present invention, it further functions to reduce thecorrosiveness of the boron compounds of the invention towards lead andcopper automotive bearings. This discovery, which is illustratedhereinafter in Examples 54 to 60, permits one, through the introductionof a single additive, to take simultaneous advantage of two desirableproperties--corrosion inhibition and oxidation inhibition.

Amines which are suitable for use as anti-oxidants or oxidationinhibitors herein have the formula (XIII): ##STR16## wherein R₅₂ and R₅₃are hydrogen or the same or different alkyl radicals having from about 1to about 30 carbon atoms, preferably from about 1 to about 20 carbonatoms, with at least one of R₅₂ and R₅₃ being an alkyl group (mostpreferably unsubstituted) having from about 1 to about 30 carbon atoms,e.g., 8 carbon atoms.

Generally, the anti-oxidants herein are incorporated into lubricantcompositions at concentrations of from 0.01 to about 2 weight percent,preferably from 0.025 to about 0.10 weight percent, sometimes up to 1.0weight percent.

It has also been found that the presence of copper compounds, dissolvedin an automotive engine oil with borates of the invention, provides forenhanced antiwear properties. This embodiment of the invention allowsfor the use of less of the borate of the invention for the same level ofdesired anti-wear protection. The preferred compounds for this use arecopper carboxylates, such as copper naphthenate, in concentrations ofabout 100 to 125 wppm as Cu. However, even higher concentrations may beused, for example, up to about 3 percent by weight if desired.

This embodiment of the invention has an additional advantage in thatcopper carboxylates, such as copper naphthenate, has anti-oxidantproperties. Other copper compounds also function in this manner, e.g.,copper oleate. And in U.S. Pat. No. 4,122,033, herein incorporated byreference in its entirety, teachings are presented for employing coppercompounds as anti-oxidants. Thus, the use of copper compounds havinganti-oxidant properties functions in two ways in lubricating oils,first, as an anti-oxidant and, second, for enhancement of the anti-wearproperties of the borate of the invention.

In addition to providing enhanced anti-wear properties, it has also beenfound that a lubrication oil comprising a borate of the invention, andparticularly a sulfurized borate of the invention, with an oil-solublecopper compound exhibits anti-oxidant properties better than expected incomparison to the anti-oxidant properties of a lubrication oilcomprising either the borate or copper compound alone.

The invention will be further described with reference to the followingexamples, which are intended to illustrate the invention, not to limitthe claims.

EXAMPLE 1

A boron-containing, heterocyclic compound is prepared by adding 20 gramsof boric acid, 95 grams of Armak Ethomeen C/12 [bis(2-hydroxyethyl)cocoamine]and 250 ml of toluene to a single-necked one literround-bottomed flask. The toluene acts as a solvent and as an azeotropefor water produced during the reaction. It should be noted that boricacid is not soluble in toluene or Ethomeen C/12. The flask is placed ina heating mantle and fitted with a Dean-Stark trap that is topped with acondenser. The mixture thus formed is then heated until it begins toreflux. Next, the mantle is adjusted to give a moderate reflux rate. Thereaction mixture is refluxed for one hour, or until the stoichiometricamount of water (12 ml.) collects in the Dean-Stark trap and all of theboric acid has dissolved, after which the toluene is distilled from thereaction product. The reaction product (103 grams) has a clear goldencolor and is a fluid liquid while hot but sets into a soft viscousmaterial when cooled to room temperature. The compound is readilysoluble in hydrocarbon solvents.

EXAMPLE 2

A boron-containing, heterocyclic compound is prepared by the followingthe procedure of Example 1 with the following substitution:

Armak Ethomeen T/12 [bis(2-hydroxyethyl) tallowamine]is substituted forthe Armak Ethomeen C/12. Substantially the same results are obtained.

EXAMPLE 3

A boron-containing, heterocyclic compound is prepared by mixing 20 gramsof boric acid, 115 grams of Armak Ethomeen 18/12 [bis(2-hydroxyethyl)octadecylamine]and, as a solvent, 250 ml of toluene in a single-neckedone liter round-bottomed flask. The flask is placed in a heating mantleand fitted with a Dean-Stark trap and water-cooled condenser. Themixture is heated under reflux for one hour, during which 12 ml of watercollects in the Dean-Stark trap. The toluene is then distilled from thereaction product. The resulting compound is readily soluble inhydrocarbon solvents.

EXAMPLE 4

The procedure of Example 3 is followed to prepare a boron compound ofthe invention with the following exception: N,N-diethanol-n-methylamine(46.3 grams) is substituted for the Armak Ethomeen 18/12. The reactionproduct thus produced is a liquid product with the consistency of honeywhen hot and becomes a waxy semi-solid when cooled to room temperature.

EXAMPLE 5

Boric acid (20 grams), N,N-diethanol-N-phenylamine (46.3 grams) and 250mls of toluene are mixed in a one liter single-necked flask to prepare aboron-containing, heterocyclic compound. The flask is equipped with aheating mantle, Dean-Stark trap and water-cooled condenser. The mixtureis heated under reflux until the reaction is completed (12 ml of watercollects), approximately one hour, and the toluene is distilled from thereaction mixture. The product thus prepared is suitable for use anextreme pressure, antiwear and friction-reducing additive forlubrication compositions.

EXAMPLE 6

A metal derivative of the reaction product yielded in Example 1 isprepared by mixing 54 grams of the product of Example 1, 400 ml oftoluene, 24.6 grams of nickel acetate and 150 ml of methanol in asingle-necked, one liter round-bottomed flask which is equipped with aheating mantle and water-cooled condenser. The mixture is refluxed forfour hours. Next, water, toluene, methanol and acetic acid are distilledfrom the reaction product. The product (59 grams) contained 7.8 weightpercent nickel as determined by emission spectroscopy and the resultingproduct is a fluid green liquid when hot, which turns into a solid uponcooling to room temperature. The product is readily soluble inhydrocarbon solvents.

EXAMPLE 7

A metal derivative of the compound of Example 2 is prepared by mixingthe reaction product of Example 2 (54 grams), 400 ml of toluene, 24grams of nickel acetate and 150 mls of methanol in a single-necked,one-liter round-bottom flask, equipped with a heating mantle, DeanStarktrap and water-cooled condenser. The mixture is refluxed for four hoursand the toluene, water and acetic acid are distilled from the reactionproduct.

EXAMPLE 8

A zinc derivative of the reaction product of Example 1 is prepared bymixing 54 grams of said reaction product with 400 ml of toluene, 19.1grams of zinc acetate and 50 ml of methanol in a single-necked,one-liter round-bottom flask, equipped with a heating mantle andwater-cooled condenser. The mixture is refluxed for four hours and thetoluene, methanol, water and acetic acid are distilled. The resultingproduct is suitable for use as an extreme pressure, anti-wear,friction-reducing additive for lubricating compositions.

EXAMPLE 9

Another metal derivative is prepared by following the procedure ofExample 7 with the following exception: zinc acetate is substituted forthe nickel acetate.

EXAMPLE 10

The extreme pressure, anti-wear and friction-reducing additives producedin Examples 1 and 6 in a 1:1 ratio mixture are mixed with 450 neutraloil and evaluated for performance. The additive mixture is mixed withthe 450 neutral oil at 5 weight percent based on the total weight of thelubricant composition. This oil mixture is compared to Arco graphitelubricant and ASTM high reference oil, SAE 20W/30 for friction reductionand extreme pressure properties.

The lubricants are tested in accordance with the procedure disclosed inASTM D3233-73 (Reapproved 1978) using a Falex lubricant tester. The testis performed by applying resistance to a revolving metal journal.Resistance is applied by two V-Blocks equipped with a ratchet mechanismwhich steadily increases pressure on the journal. The metal journal andV-Blocks are composed of steel in this example. The metal journal andV-Blocks are submerged in the lubricating composition to be tested. Theresults are indicated in the following Table 1:

                  TABLE 1                                                         ______________________________________                                        LUBRICANT                                                                     Torque on Journal lbs-in. (Newton-Meters)                                                       450 Neutral                                                                   Oil with 5 wt. %                                                              total of                                                                      Examples                                                    True     450      1 and 6                                                     Load     Neutral  Compounds           ASTM                                    Lbs.     Oil-No   in a         Arco   SAE                                     (Newtons)                                                                              Additives                                                                              1:1 ratio    Graphite                                                                             20W/30                                  ______________________________________                                        300  (1,334)  8 (0.904)                                                                              4 (0.452)  6 (0.678)                                                                            6 (0.678)                            500  (2,224) 11 (1.243)                                                                              6 (0.678)  8 (0.904)                                                                            7 (0.791)                            750  (3,336) 16 (1.808)                                                                              9 (1.017) 16 (1.808)                                                                           12 (1.356)                            1,000                                                                              (4,448) Journal  14 (1.582) 21 (2.373)                                                                           20 (2.260)                                         Shear                                                            1,250                                                                              (5,560) --       21 (2.373) 26 (2.937)                                                                           24 (2.712)                            1,500                                                                              (6,672) --       Journal    Journal                                                                              Journal                                                     Shear      Shear  Shear                                 ______________________________________                                    

It should be noted that substantially the same results are obtained whenthe nickel derivative of Example 7 is substituted for the nickelderivative of Example 6.

EXAMPLE 11

The lubricant of Example 10 containing the two compounds of theinvention is tested in accordance with the procedure set forth inExample 10 with the following exception: the metal journal and V-Blocksare constructed from cast iron. The results are indicated in thefollowing Table 2:

                  TABLE 2                                                         ______________________________________                                        LUBRICANT                                                                     Torque on Journal lbs-in. (Newton-Meters)                                              450 Neutral                                                                   Oil with 5 wt. %                                                              total of                                                                      Examples                                                             True     1 and 6                                                              Load     Compounds                                                            Lbs.     in a         Arco       ASTM                                         (Newtons)                                                                              1:1 ratio    Graphite   SAE 20W/30                                   ______________________________________                                        300  (1,334)  3 (0.339)    6 (0.678)                                                                              6 (0.678)                                 500  (2,224)  4 (0.452)    7 (0.791)                                                                              7 (0.791)                                 750  (3,336)  7 (0.791)   13 (1.469)                                                                             10 (1.130)                                 1,000                                                                              (4,448) 12 (1.356)   15 (1.695)                                                                             14 (1.582)                                 1,250                                                                              (5,560) 14 (1.582)   17 (1.921)                                                                             17 (1.921)                                 1,500                                                                              (6,672) 16 (1.808)   20 (2.260)                                                                             19 (2.146)                                 1,750                                                                              (7,784) 18 (2.034)   23 (2.599)                                                                             21 (2.373)                                 2,000                                                                              (8,896) Journal Wear 24 (2.712)                                                                             Journal Wear                               2,250                                                                              (10,008)                                                                              --           Journal Wear                                                                           --                                         ______________________________________                                    

The nickel derivative of Example 7 may conveniently be substituted forthe nickel derivative of Example 6 with substantially the same results.

EXAMPLE 12

The lubricant of Example 10 containing the two compounds of theinvention is tested in accordance with the procedure set forth inExample 10 with the following exception: the journal is constructed fromcast iron and the V-Blocks are constructed from chrome. The lubricantproperties are compared with those of Arco graphite and ASTM, SAE 20W/30lubricants. The lubricant compositions are tested in accordance with theprocedure disclosed in ASTM:D3233-73 (Reapproved 1978) using a Falexlubicant tester. The results are indicated in the following Table 3:

                  TABLE 3                                                         ______________________________________                                        LUBRICANT                                                                     Torque on Journal lbs-in. (Newton-Meters)                                              450 Neutral                                                                   Oil with 5. wt. %                                                             total of                                                                      Examples                                                             True     1 and 6                                                              Load     Compounds                                                            Lbs.     in a         Arco       ASTM                                         (Newtons)                                                                              1:1 ratio    Graphite   SAE 20W/30                                   ______________________________________                                        300  (1,334)  5 (0.565)    4 (0.452)                                                                              5 (0.565)                                 500  (2,224)  6 (0.678)    5 (0.565)                                                                              7 (0.791)                                 750  (3,336)  7 (0.791)    8 (0.904)                                                                             10 (1.130)                                 1,000                                                                              (4,448) 12 (1.356)   11 (1.243)                                                                             14 (1.582)                                 1,250                                                                              (5,560) 15 (1.695)   16 (1.808)                                                                             20 (2.260)                                 1,500                                                                              (6,672) Journal Wear Journal Wear                                                                           Journal Wear                               ______________________________________                                    

EXAMPLE 13

An extreme pressure, anti-wear and friction-reducing lubricantcomposition is prepared by mixing 5 weight percent of the zinc additiveof Example 8 with 450 neutral oil. The lubricant composition reduceswear and friction of metal components in moving contact with each otherand, in addition, lubricates said metal surfaces under extreme pressureor boundary lubrication conditions.

EXAMPLE 14 The zinc derivative additive of Example 9 is admixed with 450neutral oil at 5 percent by weight based upon the total lubricantcomposition to prepare an extreme pressure, anti-wear andfriction-reducing lubricant composition. The zinc derivative additiveimparts extreme pressure, anti-wear and friction-reducing properties tothe 450 neutral, lubricating oil. EXAMPLE 15 A lubricant compositioncontaining the nickel heterocyclic compound of Example 6 and 450 neutraloil is texted for extreme pressure, anti-wear and friction-reducingproperties in a 1973 Chevrolet 350 cu. in. displacement V-8 engine whichis run continuously for 196 hours on a single fill of the lubricatingcomposition. The lubricating oil does not contain conventional zincdialkydithiophosphate anti-wear additives. The lubricant composition isdisclosed in detail in the following Table 4:

                  TABLE 4                                                         ______________________________________                                        Compound             Weight Percent                                           ______________________________________                                        450 neutral oil      89.945                                                   Example 1 Compound   2.500                                                    Nickel Compound of Example 6                                                                       2.500                                                    Oronite OLOA 1200.sup.(A)                                                                          4.000                                                    Chlorowax 40.sup.(B) 1.000                                                    UNAD 242.sup.(C)     0.010                                                    Terephthalic Acid.sup.(D)                                                                          0.025                                                    Quinizarin.sup.(E)   0.020                                                    ______________________________________                                         .sup.(A) Oronite OLOA 1200  alkyl succinimide type ashless dispersant.        .sup.(B) Chlorowax 40  Chlorinated paraffin containing 40% chlorine.          .sup.(C) UNAD 242  Silicone type defoamant with kerosene.                     .sup.(D) Terephthalic acid  Corrosion inhibitor.                              .sup.(E) Quinizarin  Antioxidant.                                        

The Chevrolet engine is programmed to run in a repeating cycle thataveraged approximately 40 MPH. The cycle is disclosed in the followingTable 5:

                  TABLE 5                                                         ______________________________________                                        Cycle RPM     Speed MPH (Kilometers/Hr.)                                                                       Time (MIN.)                                  ______________________________________                                        1       700   0         (0)        2.0                                        2     1,700   45        (72.4)     3.0                                        3     1,200   30        (48.3)     4.0                                        4     2,225   60        (96.5)     0.12                                       5     2,400   65        (104.6)    3.0                                        ______________________________________                                    

After the 196 hour engine test is completed, several areas in the enginewhich are subject to wear are closely examined. These areas include:main bearings, top end bearings, cam shaft bearings, valve lifters andcam shaft lobes.

The length of the engine run is equivalent to approximately 8,000 milesof driving. A detailed examination of the above-described componentsindicated no abnormal or excessive wear.

EXAMPLE 16

The extreme pressure, anti-wear and friction-reducing additives ofExample 1 and Example 2 are individually mixed with SAE 10W/40 motor oilcontaining 0.15 weight percent of phosphorus and 0.17 weight percent ofzinc. In addition, the motor oil contains 0.21 weight percent ofcalcium.

The resulting lubricant compositions are tested in accordance with theprocedure disclosed in ASTM D3233-73 (Reapproved 1978) using a Falexlubricant tester. The test, in accordance with the above ASTMdesignation, is performed by applying resistance to a revolving metaljournal. A rachet mechanism movably attached to two V-blocks appliesresistance by steadily increasing pressure on the journal. The metaljournal and V-blocks (steel) are submerged in the lubricant compositionto be tested. The results are set forth in the following Table 6:

                  TABLE 6                                                         ______________________________________                                        Torque on Journal, lb.-in (Newtons-Meters)                                                         SAE 10W/40.sup.(a)                                                                        SAE 10W/40.sup.(a)                                     SAE 10W/   Plus 1 wt. %                                                                              Plus 1 wt. %                                 True Load 40.sup.(a) Without                                                                       of Ex. 1    of Ex. 2                                     lbs (Newtons)                                                                           Additive   Compound    Compound                                     ______________________________________                                        100  (445)    8      (0.904)                                                                             71/2 (0.847)                                                                              71/2 (0.847)                           250  (1,112)  12     (1.356)                                                                             10   (1.130)                                                                              9    (1.017)                           500  (2,224)  19     (2.147)                                                                             15   (1.695)                                                                              14   (1.582)                           750  (3,336)  22     (2.486)                                                                             18   (2.034)                                                                              19   (2.146)                           1,000                                                                              (4,448)  25     (2.825)                                                                             22   (2.486)                                                                              22   (2.486)                           1,250                                                                              (5,560)  35     (3.954)                                                                             25   (2.825)                                                                              25   (2.825)                           1,500                                                                              (6,672)  Journal    27   (3.050)                                                                              27   (3.050)                                           Shear                                                           1,750                                                                              (7,784)  --         Journal   33   (3.728)                                                        Shear                                                2,250                                                                              (10,008) --         --        Journal                                                                       Shear                                      ______________________________________                                         .sup.(a) Union Super Motor Oil, marketed commercially by the Union Oil        Company of California.                                                   

EXAMPLE 17

A metal heterocyclic compound is prepared by following the procedure ofExample 6 with the following changes: 31 grams of reaction productyielded in Example 1 is mixed with 19 grams of lead (II) acetate, 150ml. of toluene and 25 ml of methanol. The mixture is refluxed for 2hours, after which, the toluene, methanol, water and acetic acid(produced from acetate) are distilled using conventional techniques andapparatus. The resulting lead-containing product (32.6 grams) is agolden colored oil with the consistency of honey.

EXAMPLE 18

The extreme pressure, anti-wear and friction-reducing additive, leadderivative produced in accordance with the procedure of Example 17 isblended with 450 neutral oil at 5 percent by weight based on the totalweight of the lubricant composition. The above lubricant composition iscompared to Arco graphite lubricant and ASTM high reference oil, SAE20W-30 for friction reduction and extreme pressure properties.

The lead derivative and 450 neutral oil mixture is compared to Arcographite and ASTM, SAE 20W/30 in accordance with the procedure disclosedin ASTM:D3233-73 (Reapproved 1978) using a Falex lubricant tester. Thetest is performed by applying resistance to a revolving metal journal.Resistance is applied by two V-Blocks equipped with a retchet mechanismwhich steadily increases pressure on the journal. The metal journal andV-Blocks are composed of steel in this example. The metal journal andV-Blocks are submerged in the lubricating composition to be tested. Theresults are indicated in the following Table 7:

                  TABLE 7                                                         ______________________________________                                        Torque on Journal lbs-in. (Newton-Meters)                                                450 Neutral                                                                   Oil with                                                           True Load  Lead        Arco       ASTM                                        Lbs. (Newtons)                                                                           Derivative  Graphite   SAE 20W/30                                  ______________________________________                                        300   (1,334)  7     (0.791) 6    (0.678)                                                                             6    (0.678)                          500   (2,224)  11    (1.243) 8    (0.904)                                                                             7    (0.791)                          750   (3,336)  14    (1.582) 16   (1.808)                                                                             12   (1.356)                          1,000 (4,448)  20    (2.260) 21   (2.373)                                                                             20   (2.260)                          1,250 (5,560)  23    (2.599) 26   (2.937)                                                                             24   (2.712)                          1,500 (6,672)  40    (4.520) Journal Shear                                                                          Journal Shear                           1,750 (7,784)  85    (9.605)                                                  2,000 (8,896)  94    (10.622)                                                 2,250 (10,000) 90    (10.170)                                                 2,500 (11,120) 71    (8.023)                                                  2,750 (12,232) 79    (8.927)                                                  3,000 (13,344) 70    (7.345)                                                  3,250 (14,456) 70    (7.345)                                                  Stopped due to inability to increase load.                                    ______________________________________                                    

EXAMPLE 19

A copper-heterocyclic compound is prepared by adding 62 grams of theboron-containing, heterocyclic reaction product yielded in Example 1,150 ml of toluene, 50 ml of water and 18.2 grams of cupric acetate to a500 ml., single-necked round-bottom flask equipped with a Dean-Starktrap and condenser. The mixture is refluxed for 8 hours, after which,water, toluene and produced acetic acid (from acetate) are distilledleaving 68 grams of a green solid.

EXAMPLE 20

The copper derivative additive produced in Example 19 is admixed with450 neutral oil at 5 weight percent based on the total weight of thelubricant composition and evaluated for performance in accordance withthe procedure of Example 18 with the following exception: the lubricantproperties of the copper derivative-450 neutral oil mixture are comparedwith those of 450 neutral oil and SAE 10W/40 lubricants. The results areindicated in the following Table 8:

                  TABLE 8                                                         ______________________________________                                        Torque on Journal lbs.-in (Newton-Meters)                                               450 Neutral Oil                                                                             450 Neutral                                           True Load with Copper Com-                                                                            Oil Without                                                                              SAE                                        lbs. (Newtons)                                                                          pound from Ex. 19                                                                           Additive   10W-40                                     ______________________________________                                        300  (1,334)  9       (1.017) 10   (1.130)                                                                             --                                   500  (2,224)  11      (1.243) 15   (1.695)                                                                             17  (1.921)                          750  (3,336)  17      (1.921) 23   (2.599)                                                                             21  (2.373)                          1,000                                                                              (4,448)  20      (2.260) Journal  28  (3.163)                                                          Shear                                           1,250                                                                              (5,560)  28      (3.163)          33  (3.728)                            1,500                                                                              (6,672)  55      (6.214)        Journal                                                                       Shear                                    1,750                                                                              (7,784)  55      (6.214)                                                 2,000                                                                              (8,896)  55      (6.214)                                                 2,250                                                                              (10,008) 60      (6.779)                                                 2,500                                                                              (11,120) 65      (7.345)                                                 2,750                                                                              (12,232) 70      (7.909)                                                 3,000                                                                              (13,344) 75      (8.474)                                                 3,250                                                                              (14,456) 80      (9.038) (Stopped for inspection)                        ______________________________________                                    

EXAMPLE 21

The boron-containing, heterocyclic compound,1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane, isprepared by adding 14,889 grams of cocoamine.sup.(1) and 17,516 grams ofstyrene oxide to a 65 liter round bottomed flask that contains 13 litersof toluene and 1 liter of water. The flask is placed in a heating mantleand fitted with a water-cooled condenser. The mixture thus formed isheated until it begins to reflux. Next, the temperature is adjusted togive a moderate reflux rate and the reaction mixture is refluxed for 24hours. The reaction mixture is cooled to room temperature and 4,595grams of boric acid are added to the flask. Then, the flask is equippedwith a Dean-Stark trap topped with a water-cooled condenser and thereaction mixture is refluxed until water stops collecting in the trap.Toluene is distilled from the reaction product to an end point at atemperature of 400° F. (204° C.). The reaction produces 34,373 grams of1-hydroxy-3,7-diphenyl-5-coco-5-aza-1 -bora-2,8-dioxacyclooctane.

EXAMPLE 22

A boron-containing, heterocyclic compound is prepared by adding 17,605grams of tallowamine.sup.(2) and 15,362 grams of styrene oxide to a65-liter round-bottomed flask that contains 11.34 liters of toluene and1 liter of water. The flask is fitted with a water-cooled condenser andplaced in a heating mantle. The mixture thus formed is refluxed at amoderate rate for 24 hours. The reaction is cooled to room temperatureand 4,033 grams of boric acid are added to the flask. Next, the flask isfitted with a Dean-Stark trap, topped with a water-cooled condenser andthe reaction mixture is refluxed until water stops collecting in thetrap. Toluene is distilled from the reaction product to an end pointtemperature of 400° F. (204° C.). The reaction produces 34,695 grams of1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 23

1-hydroxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane isprepared by adding 13,502 grams of dodecylamine and 17,516 grams ofstyrene oxide to a 65-liter round-bottomed flask that contains 13.34liters of toluene and 1 liter of water. The flask is placed in a heatingmantle and fitted with a water-cooled condenser. The mixture thus formedis heated until it begins to reflux. Next, the temperature is adjustedto give a moderate reflux rate and the reaction mixture is refluxed for24 hours. The reaction mixture is cooled to room temperature and 4,595grams of boric acid are added to the flask. Then, the flask is equippedwith a Dean-Stark trap topped with a water-cooled condenser and thereaction mixture is refluxed until water stops collecting in the trap.Toluene is distilled from the reaction product to an end-pointtemperature of 400° F. The reaction produces 32,986 grams of1-hydroxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 24

The compound,1-hydroxy-3,6-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane, isprepared by adding 21 grams of boric acid with 61.7 grams ofdodecylamine, 89.3 grams of para methylstyrene oxide and 250 ml oftoluene to a single-necked, one-liter, round-bottomed flask. The tolueneacts as a solvent and as an azeotrope for water produced during thereaction. It should be noted that boric acid is not soluble in toluene.The flask is placed in a heating mantle and fitted with a Dean-Starktrap that is topped with a water-cooled condenser. The mixture thusformed is heated until it begins to reflux. Next, the mantle heat isadjusted to give a moderate reflux rate. The reaction mixture isrefluxed for one hour, or until the stoichiometric amount of water (12ml) collects in the Dean-Stark trap and all of the boric acid hasdissolved, after which the toluene is distilled from the reactionproduct. The reaction produces 160 grams of product.

EXAMPLE 25

The compound,1-hydroxy-3,7-dimethyl-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane, is prepared by following the procedure of Example23 with the following substitution:

Alpha methyl styrene oxide is substituted for the styrene oxide withsubstantially the same results.

EXAMPLE 26

Boric acid (21 grams), para-tertiary-butyl styrene oxide (119.3 grams),dodecylamine (61.7 grams) and 250 ml of toluene are mixed in aone-liter, single-necked flask to prepare1-hydroxy-3,7-para-tertiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane.The flask is equipped with a heating mantle, Dean-Stark trap andwater-cooled condenser. The mixture is heated under reflux until thereaction is completed; 12 ml of water collects in the Dean-Stark trap.Next, toluene is distilled from the reaction mixture. The product thusprepared is suitable for use as an extreme pressure, anti-wear andfriction-reducing additive for lubricating compositions.

It should be noted that the other primary amines herein may besubstituted for the dodecylamine above, to form the corresponding boronheterocyclic compound.

EXAMPLE 27

A copper derivative of1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane isprepared by following the procedure Example 21 with the followingexception: the above-described compound (47 grams), 100 ml of toluene,20 ml of triethyl amine and 10 grams of cupric acetate are mixed in asingle-necked, 500 ml round-bottomed flask, equipped with a heatingmantle and water-cooled condenser. The mixture is refluxed for 16 hours,then filtered and the toluene, amine, water and acetic acid (produced insitu) are distilled from the reaction product. Using theabove-procedure, copperdi-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane] isproduced.

EXAMPLE 28

A nickel derivative of1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane isprepared by following the procedure of Example 27 with the followingexception:

An equivalent amount of nickel acetate is substituted for the cupricacetate. The reaction produces nickeldi-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane].

EXAMPLE 29

Lead di-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane]isprepared in accordance with the procedure of Example 21 with thefollowing exception:

The reaction product produced in Example 21 (23.5 grams), 100 ml oftoluene, 9.5 grams of lead acetate and 10 ml of triethylamine are mixedin a single-necked 500 ml round bottomed flask, equipped with awater-cooled condenser and heating mantle. The mantle heat is adjusteduntil a moderate rate of reflux is obtained. The mixture thus formed isrefluxed for 18 hours. Next, the mixture is filtered, and toluene,water, triethylamine and acetic acid (produced in the reaction) aredistilled from the reaction product. The reaction produces leaddi-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 30

Iron di-(1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane) isprepared according to the procedure of Example 21 with the followingexception:

A mixture comprising 23.5 grams of the reaction product produced inExample 21, 100 ml of toluene, 4.3 grams of ferrous acetate and 10 ml oftriethylamine are introduced into a single-necked, 500-ml,round-bottomed flask, equipped with a water-cooled condenser and heatingmantle and Dean-Stark trap.

EXAMPLE 31

A boron compound of the invention is prepared by adding 17,093 grams ofoctadecylamine and 15,362 grams of styrene oxide to a 65-liter,round-bottomed flask that contains 13 liters of toluene and 1 liter ofwater. The flask is fitted with a water-cooled condenser and placed in aheating mantle. The mixture thus formed is refluxed at a moderate ratefor 24 hours. The reaction is cooled to room temperature and 4,033 gramsof boric acid are added to the flask. Next, the flask is fitted with aDean-Stark trap, topped with a water-cooled condenser and the reactionmixture is refluxed until water stops collecting in the trap. Toluene isdistilled from the reaction product to an end-point temperature of 400°F. The reaction produces 34,183 grams of1-hydroxy-3,7-diphenyl-5-octadecyl-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 32

The procedure of Example 31 is followed to produce1-hydroxy-3,7-diphenyl-5-phenyl-5-aza-1-bora-2,8-dioxacyclooctane withthe following exception:

An equivalent amount of phenylamine is substituted for octadecylamine.

EXAMPLE 33

Zinc di-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane]isproduced according to the procedure of Example 27 except that anequivalent amount of zinc acetate is substituted for the cupric acetate.

EXAMPLE 34

Tin di-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane] isprepared by substituting an equivalent amount of tin acetate for thecupric acetate in Example 27.

EXAMPLE 35

Leaddi-[1-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]isprepared in accordance with the procedure of Example 23 with thefollowing exception:

The reaction product produced in Example 23 (23.95 grams), 100 ml oftoluene, 9.5 grams of lead acetate, and 10 ml of triethylamine are mixedin a single-necked, 500-ml, round-bottom flask, equipped with awater-cooled condenser, heating mantle and Dean-Stark trap. The mantleheat is adjusted until a moderate rate of reflux is obtained. Themixture thus formed is refluxed for 18 hours. Next, the mixture isfiltered and the toluene, triethylamine, water and acetic acid (producedin-situ) are distilled from the reaction product. The reaction producesleaddi[-1-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane].

EXAMPLE 36

A nickel derivative of1-hydroxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane isprepared by following the procedure of Example 35 with the followingexception:

An equivalent amount of paramethyl styrene oxide is substituted forstyrene oxide and nickel acetate is substituted for lead acetate. Thereaction produces nickeldi[-1-oxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8dioxacyclooctane].

EXAMPLE 37

Irondi-[1-oxy-3,7-di-para-tertiary-butyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]is prepared according to the procedure of Example 26 with the followingexception:

A mixture comprising 28.4 grams of the reaction product produced inExample 26, 100 ml of toluene, 4.3 grams of ferrous acetate and 10 ml oftriethylamine are introduced into a single-necked, 500-ml, round-bottomflask, equipped with a Dean-Stark trap, water-cooled condenser andheating mantle. The heating mantle is adjusted to give a moderate rateof reflux of the reaction mixture. The mixture is refluxed for 18 hours,filtered, and the toluene, triethylamine, water and acetic acid(produced in-situ) are distilled from the reaction product.

EXAMPLE 38

Zincdi-[1-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]isproduced according to the procedure of Example 35 except that zincacetate is substituted for lead acetate.

EXAMPLE 39

Tindi-[1-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]isprepared by substituting tin acetate for lead acetate in Example 35.

EXAMPLES 40 TO 46

Extreme pressure, anti-wear and friction-reducing additives producedaccording to the procedure of Examples 21, 27, 29, 30, 33 and 34 aremixed with separate portions of 450 neutral oil at concentrations of 2weight percent.

Each lubricant composition is tested in accordance with the proceduredisclosed in ASTM:D3233-73 (Reapproved 1978) using a Falex lubricanttester. The test, in accordance with the above ASTM designation, isperformed by applying resistance to a revolving metal journal. A rachetmechanism movably attached to two V-blocks applies resistance bysteadily increasing pressure on the journal. The metal journal andV-blocks (steel) are submerged in the lubricant composition to betested. A summary of the results obtained is disclosed in the followingTable 9:

                                      TABLE 9                                     __________________________________________________________________________    TORQUE ON JOURNAL LB.-IN. (NEWTON-METERS)                                             Example                                                                             41   42   43   44   45   46                                             40    Oil with                                                                           Oil with                                                                           Oil with                                                                           Oil with                                                                           Oil with                                                                           Oil with                               True Load                                                                             (450 Neutral                                                                        Additive                                                                           Additive                                                                           Additive                                                                           Additive                                                                           Additive                                                                           Additive                               lbs. (Newtons)                                                                        Oil)  of Ex. 21                                                                          of Ex. 27                                                                          of Ex. 29                                                                          of Ex. 30                                                                          of Ex. 33                                                                          of Ex. 34                              __________________________________________________________________________      300 (1,334)                                                                          9 (1.017)                                                                           7 (0.791)                                                                         11 (1.243)                                                                          9 (1.017)                                                                         10 (1.130)                                                                          9 (1.017)                                                                          7 (0.791)                               500 (2,224)                                                                         12 (1.356)                                                                           9 (1.017)                                                                         15 (1.695)                                                                         15 (1.695)                                                                         15 (1.695)                                                                         14 (1.582)                                                                          9 (1.017)                               750 (3,336)                                                                         Journal                                                                             17 (1.921)                                                                         21 (2.373)                                                                         21 (2.373)                                                                         22 (2.486)                                                                         22 (2.486)                                                                         16 (1.808)                                     Shear                                                                   990 (4,404)                                                                         --    --   --   --   --   Journal                                                                            --                                                                       Shear                                       1,000 (4,448)                                                                         --    24 (2.712)                                                                         28 (3.163)                                                                         30 (3.389)                                                                         28 (3.163)                                                                         --   19 (2.147)                             1,050 (4,670)                                                                         --    --   Journal                                                                            Journal                                                                            Journal                                                                            --   23 (2.599)                                                Shear                                                                              Shear                                                                              Shear                                            1,250 (5,560)                                                                         --    Journal                                                                            --   --   --   --   26 (2.937)                                           Shear                                                           1,500 (6,672)                                                                         --    --   --   --   --   --   Journal                                                                       Shear                                  1,750 (7,784)                                                                 __________________________________________________________________________     The above data indicate that the boroncontaining, heterocyclic compounds      described above impart extreme pressure properties to 450 neutral oil at      concentrations of 2 weight percent.                                      

EXAMPLES 47 AND 48

The extreme pressure, anti-wear and friction-reducing additive producedin accordance with the procedure of Example 21 is mixed at aconcentration of 2 weight percent with SAE 30 motor oil which contains0.05 weight percent phosphorus. A sample of the SAE 30 motor oil whichdoes not contain the additive of Example 21 is used as a control. Thiscontrol was blended 6.5 volume percent (7.05 weight percent) AmocoPCO-059 in Union 450 neutral. (See footnote (E) in Table 12 hereafter.)

Each lubricant composition is tested in accordance with the proceduredisclosed in ASTM D3233-73 (Reapproved 1978) using a Falex lubricanttester. A summary of the results in disclosed in the following Table 10:

                  TABLE 10                                                        ______________________________________                                        Torque on Journal lbs.-in (Newton-Meters)                                             Example                                                                         47            48                                                    True Load Control (SAE 30                                                                             SAE 30 Motor Oil                                      lbs. (Newtons)                                                                          Motor Oil)    with Additive of Ex. 21                               ______________________________________                                        300  (1,334)  9        (1.017)                                                                              8       (0.904)                                 500  (2,224)  14       (1.582)                                                                              12      (1.356)                                 750  (3,336)  20       (2.260)                                                                              17      (1.921)                                 950  (4,404)  Journal Shear --                                                1,000                                                                              (4,448)  --            22      (2.486)                                   1,250                                                                              (5,560)  --            28      (3.163)                                   1,400                                                                              (6,227)  --            Journal Shear                                     ______________________________________                                    

The extreme pressure property of SAE 30 motor oil is substantiallyenhanced in Table 10 above when 2 weight percent of1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane is addedto said SAE 30 motor oil.

EXAMPLE 49

A copper corrosion inhibitor comprising1,3,4-thiadiazole-2,5-bis(dodecyldisulfide) is prepared by chlorinating284 grams of n-dodecyl mercaptan in 0.6 liter of carbon tetrachloridewith 1.47 moles of chlorine over a two-hour period at a temperature ofabout 23° F. (-5° C.) to about 32° F. (0° C.). Next, sulfenyl chloridewhich forms as a reaction product is stripped with nitrogen to removehydrogen chloride, and the resultant compound is added to 86 grams of a2,5-dimercapto-1,3,4-thiadiazole slurry. The mixture is heated at 86° F.(30° C.) for 1 and 1/2 hours and the resultant compound(1,3,4-thiadiazole-2,5-bis(dodecyldisulfide) is recovered by washingwith water and sodium bicarbonate and vacuum stripping to remove carbontetrachloride.

EXAMPLE 50

The procedure of Example 49 is followed to prepare1,3,4-thiadiazole-2,5-bis (octyldisulfide) with the following exception:octyl mercaptan is substituted for the dodecylmercaptan.

EXAMPLE 51

The oxidation inhibitor, thiodiethyl bis-(3,5-di-t-butyl-4-hydroxy)hydrocinnamate, is prepared by melting together 17.95 weight percent ofbeta,beta'-dihydroxydiethyl sulfide, 81.41 weight percent of(3,5-di-t-butyl-4-hydroxy) hydrocinnamate acid and 0.64 weight percentof sodium methylate under a nitrogen atmostphere at 266° F. (130° C.)for two and one-half hours. Methanol thus formed is separated from thereaction mixture and condensed in a dry-ice trap using nitrogen gas as acarrier. The reactants are heated at 149° F. (65° C.) for three hoursand the reaction product is dissolved in warm benzene, filtered and thebenzene filtrate is washed three times with saturated sodium chloridesolution. The filtrate is, next, dried over anhydrous sodium sulfate andthe solvent evaporated using conventional techniques. Thiodiethylbis-(3,5-di-t-butyl-4-hydroxy) hydrocinnamate is isolated and purifiedby successive recrystallization from hexane and a mixture of hexane andt-butanol.

EXAMPLE 52

The oxidation inhibitor, bis(dithiobenzil) iron (II), is prepared byadding 400 grams of benzoin and 600 grams of phosphorous sulfide to asingle-necked, 5-liter, round-bottomed flask equipped with heatingmantle and water-cooled condenser and containing 1,500 ml of dioxane.The mixture thus formed is refluxed for two hours. Next, 200 grams ofhydrated ferrous chloride dissolved in 500 ml of water is added to the 5liter flask and the mixture is heated on a steam bath at 212° F. (100°C.) for 2 hours. The reaction product thus formed (169.5 grams) isfiltered and washed with methanol.

EXAMPLE 53

Dodecylamino di(phenylethylate) hydrogen borate is prepared by adding34.85 pounds (15,808 grams) of dodecylamine (1 equivalent) and 41.0pounds (18,597 grams) of styrene oxide (2 equivalents) to a 17 U.S.gallon (64.3 liters) round bottomed flask equipped with a water-cooledcondenser and containing 3 U.S. gallons (11.36 liters) toluene and 1liter of water. The reaction is exothermic and begins immediately uponaddition of the above reactants. Additional heat is applied and thereaction mixture is refluxed for a total of 24 hours; however, as littleas 2 hours may result in complete reaction. The reaction is cooled toroom temperature, 10.49 pounds (4,758.16 grams) of boric acid (1equivalent) is added and the flask is equipped with a Dean-Stark trap.Heat is again applied and the reaction mixture refluxed until waterstops collecting in the trap. Toluene is, then, distilled from thereaction product at a temperature of 400° F. (204° C.) or less. About 6liters of water collect in the Dean-Stark trap. The reaction producesapproximately 75 pounds (34,019 grams) of product.

EXAMPLES 54 TO 60

A lubricant composition containing dodecylamino di(phenylethylate)hydrogen borate, 1,3-4-thiodiazole-2,5-bis(octyldisulfide), terephthalicacid, and thiodiethyl bis-(3,5-di-t-butyl-4-hydroxy) hydrocinnamate istested for copper and lead corrosion inhibition and anti-oxidantproperties using a single-cylinder Labeco CLR Test Engine equipped withsintered copper (65 wt. %)/lead (35 wt. %) connecting rod bearings, inaccordance with the procedure of Federal Test Method Standard No. 791B,method 3405.2. The same lubricant composition, but containingbis(dithiobenzil)iron(II) substituted for the hydrocinnamate compound,is also tested by the same procedure.

The copper-lead corrosion tests are conducted in accordance with thetest conditions of the following Table 11:

                  TABLE 11                                                        ______________________________________                                        Operating Conditions                                                          ______________________________________                                        Test Duration, Hours   40                                                     Speed, RPM             3150 ± 25                                           Load, BHP              6.5a                                                   (KW)                   (4.85)                                                 Fuel, Flow, Lb/Hr.     4.75 ± 0.25                                         (gm/Hr.)               (2,155 ± 5)                                         Air/Fuel Ratio         14.0 ± 0.5                                          Jacket Outlet Coolant Temp., °F.                                                              200 ± 2                                             (°C.)           (93.33 ± 1.11)                                      Gallery Oil Temp., °F.                                                                        290 ± 2                                             (°C.)           (143.33 ± 1.11)                                     Spark Advance, BTDC    35 ± 1                                              Oil Pressure, PSIG     40 ± 2                                              (atmospheres)          (3.72)                                                 Crankcase Vacuum, in. H.sub.2 O                                                                      2 ± 0.5                                             (cm. H.sub.2 O)        (5.08 ± 1.27)                                       Exhaust Back Pressure, in. Hg.                                                                       0.5 ± 0.5                                           (cm. Hg)               (1.27 ± 1.27)                                       Crankcase Off-Gas, CFH 30 ± 1                                              (CMH)                  (0.83 ± .03)                                        Oil Charge, Pints      3.5                                                    (Liters)               (1.66)                                                 ______________________________________                                    

The test is conducted by charging 3.5 pints (1.66 liters) of the testlubricant to the engine sump. Test duration consists of 40 hoursoperation at the prescribed test conditions of Table 11 above. When theprescribed gallery oil temperature is reached, the test time begins.Interim oil adjustments are made at the end of 10, 20 and 30 hours oftest operation. A copper/lead bearing weight loss (BWL) of about 40 mgof lower is considered acceptable. All of the tests are conducted onblends based upon the control using SAE 30 motor oil further containingthe additives and/or compounds, at the concentrations in the followingTable 12:

                                      TABLE 12                                    __________________________________________________________________________          Heterocyclic                            CRC L-38                              Compound                                                                             Copper Corrosion                                                                              Anti-       Amoco.sup.(E)                                                                      Engine Test                           of Ex. 53.sup.(A)                                                                    Inhibitor.sup.(B)                                                                      Terephthalic                                                                         Oxidant                                                                            Phosphorous                                                                          PCO-059                                                                            40 hours                        Example                                                                             (Wt. %)                                                                              (Wt. %)  Acid (Wt. %)                                                                         (Wt. %)                                                                            (Wt. %)                                                                              (Vol. %)                                                                           (BWL, mg).sup.(F)               __________________________________________________________________________    Control 47                                                                          --     --       --     --   0.05   6.5  24.0                            54    2.12   --       --     --   0.05   6.5  93                              55    2.12   0.050    0.01   --   0.05   6.5  43.0                            56    2.12   0.075    0.01   --   0.05   6.5  40.0                            57    2.12   0.075    0.01   --   0.05   6.5  33.4                            58    2.00   0.03      0.006 --   0.05   6.5  38                              59    2.12   0.075    0.01    0.05.sup.(C)                                                                      0.05   6.5  26.4                            60    2.00   0.075    0.01    0.05.sup.(D)                                                                      0.05   6.5  34.8                            __________________________________________________________________________     .sup.(A) Dodecylamino di(phenylethylate) hydrogen borate.                     .sup.(B) Copper Corrosion Inhibitor = A mixture of 83 weight percent          1,3,4thiodiazole-2,5-bis(octyldisulfide) and 17 weight percent of 2           mercapto5 octyldithio1,3,4-thiadiazole, marketed under the Tradename of       Amoco 150 by the Amoco Oil Company.                                           .sup.(C) Thiodiethyl bis(3,5-di-t-butyl-4-hydroxy) hydrocinnamate.            .sup.(D) Bis(dithiobenzil)iron(II).                                           .sup.(E) Amoco PCO059 = detergent/dispersant package marketed commerciall     by the Amoco Oil Company.                                                     .sup.(F) BWL = bearing weight loss.                                      

EXAMPLE 61

The bis(hydrocarbyloxy methylated) boron-containing heterocycliccompound, 1-hydroxy-3,7-di(methyl phenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane, is prepared by adding278.5 grams of cocoamine and 450.5 grams of cresyl glycidyl ether to a2-liter round-bottomed flask that contains 250 ml of toluene and 22 mlof water. The flask is placed in a heating mantle and fitted with awater-cooled condenser. The mixture thus formed is heated until itbegins to reflux. Next, the temperature is adjusted to give a moderatereflux rate and the reaction mixture is refluxed for 18 hours. Thereaction mixture is cooled to room temperature and 86.0 grams of boricacid are added to the flask. Then, the flask is placed in a heatingmantle and fitted with a water-cooled condenser. The mixture thus formedis heated until it begins to reflux. Next, the temperature is adjustedto give a moderate reflux rate and the reaction mixture is refluxed for18 hours. The reaction mixture is cooled to room temperature and 86.0grams of boric acid are added to the flask. Then the flask is equippedwith a Dean-Stark trap topped with a water-cooled condenser and thereaction mixture is refluxed until water stops collecting in the trap.Toluene is distilled from the reaction product to an end-pointtemperature of 400° F. (204° C.). The reaction produces 758.5 grams of1-hydroxy-3,7-di(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 62

The bis(hydroxycarbyloxymethylated) boron-containing, heterocycliccompound,1-hydroxy-3,7-di(methylphenoxymethyl)-5-oleyl-5-aza-1-bora-2,8-dioxacyclooctane,is prepared by adding 55.6 grams of oleyl amine and 66.0 grams of cresylglycidyl ether to a 1-liter round-bottomed flask that contains 250 ml oftoluene. The flask is placed in a heating mantle and fitted with awater-cooled condenser. The mixture thus formed is heated until itbegins to reflux. Next, the temperature is adjusted to give a moderatereflux rate and the reaction mixture is refluxed for 18 hours. Thereaction mixture is cooled to room temperature and 12.4 grams of boricacid are added to the flask. Then, the flask is equipped with aDean-Stark trap topped with a water-cooled condenser and the reactionmixture is refluxed until water stops collecting in the trap. Toluene isdistilled from the reaction product to an end point temperature of 400°F. (204° C.). The reaction produces 97 grams of1-hydroxy-3,7-di-(methylphenoxymethyl)-5-oleyl-5-aza-1-bora-2,8-dioxacyclooctane.

EXAMPLE 63

The compound, 1-hydroxy-3,7-di(methyl phenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane, is prepared inaccordance with the procedure of Example 61 with. the followingexception: one mole of dodecylamine is substituted for each mole ofcocoamine used.

EXAMPLE 64

The compound, 1-hydroxy-3,7-di(methyl phenoxymethyl)-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane, is prepared inaccordance with the procedure of Example 62 with the followingexception: one mole of tallowamine is substituted for each mole of oleylamine used.

EXAMPLE 65

A copper derivative of 1-hydroxy-3,7-di(methyl phenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane is prepared byfollowing the procedure of Example 61 with the following exception: thecompound of Example 61 (47 grams), 100 ml of toluene, 20 ml of triethylamine and 10 grams of cupric acetate are mixed in a single-necked, 500ml round bottom flask, equipped with a heating mantle, Dean-Stark trapand water-cooled condenser. The mixture is refluxed for 16 hours, thenfiltered and the toluene, amine, water and acetic acid (produced insitu) are distilled from the reaction product. Uslng the aboveprocedure, copper di[1-oxy-3,7-di(methyl phenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane] is produced.

EXAMPLES 66 TO 71

The compound1-hydroxy-3,7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctaneproduced in accordance with the procedure of Example 61 is tested forextreme pressure, anti-wear and friction-reducing properties admixedwith separate portions of 450 neutral oil and SAE 30 motor atconcentrations of 1 and 2 weight percent respectively. Samples of 450neutral oil and the control SAE 30 motor oil (Example 47) without thecompound1-hydroxy-3,7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctaneserve as controls of the experiments.

Each lubricant composition is tested in accordance with the proceduredisclosed in ASTM:D3233-73 (Reapproved 1978) using a Falex lubricanttester. The test, in accordance with the above ASTM designation, isperformed by applying resistance to a revolving metal journal. A rachetmechanism movably attached to two V-blocks applies resistance bysteadily increasing pressure on the journal. The metal journal andV-blocks(steel) are submerged in the lubricant composition to be tested.A summary of the results obtained is disclosed in the following Table13:

                                      TABLE 13                                    __________________________________________________________________________    TORQUE ON JOURNAL LB.-IN. (NEWTON-METERS)                                             Example                                                                             67       68       69    70       71                                     66    450 Neutral                                                                            450 Neutral                                                                            SAE 30                                                                              SAE 30 Motor                                                                           SAE 30 Motor                   True Load                                                                             450 Neutral                                                                         Oil with 1 wt. %                                                                       Oil with 2 wt. %                                                                       Motor Oil                                                                           Oil with 1 wt. %                                                                       Oil with 2 wt. %               Lbs. (Newtons)                                                                        Oil   Additive of Ex. 61                                                                     Additive of Ex. 61                                                                     (Ex. 47)                                                                            Additive of Ex. 61                                                                     Additive of Ex.                __________________________________________________________________________                                                   61                             300 (1,334)                                                                            8 (0.904)                                                                           7 (0.791)                                                                              6 (0.678)                                                                             12 (1.356)                                                                           7 (0.791)                                                                              8 (0.904)                     500 (2,224)                                                                           14 (1.582)                                                                          10 (1.130)                                                                             10 (1.130)                                                                             17 (1.921)                                                                          12 (1.356)                                                                             11 (1.243)                     600 (2,669)                                                                           xxx.sup.(1)                                                                         --       --       --    --       --                             750 (3,336)   18 (2.034)                                                                             17 (1.921)                                                                             30 (3.389)                                                                          16 (1.808)                                                                             15 (1.695)                     800 (3,558)   --       --       xxx   --       --                             1,000 (4,448) xxx      20 (2.260)     25 (2.825)                                                                             20 (2.260)                     1,100 (4,893)          xxx            --       --                             1,250 (5,560)                         xxx      26 (2.937)                     1,500 (6,672)                                  xxx                            __________________________________________________________________________     .sup.(1) xxx indicates failure occurred with the journal scoring and the      shear pin breaking.                                                      

As shown in Table 13, the addition of1-hydroxy-3,7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctaneto 450 neutral oil and to the control SAE 30 motor oil (Example 47) atconcentrations of one and two weight percent, respectively, impartsextreme pressure properties to the oils.

EXAMPLE 72

A lubricant composition is tested for copper and lead corrosioninhibition properties using a single-cylindered Labeco CLR Test Engineequipped with sintered copper (65 wt. %)/lead (35 wt. %) connecting rodbearings, in accordance with the procedure of Federal Test MethodStandard No. 791B, Method 3405.2.

The test is conducted in accordance with the test conditions of Table 11in previous Examples 54 to 60.

In addition, the test is conducted by charging 3.5 pints (1.7 liters) ofthe test lubricant to the engine sump. Test duration consists of 40hours operation at the prescribed test conditions of Table 11 above.When the prescribed gallery oil temperature is reached, the test timebegins. Interim oil adjustments are made at the end of 10, 20 and 30hours of test operation. A copper/lead bearing weight loss (BWL) ofabout 40 mg or lower is considered acceptable.

The lubricant composition tested in this Example 72 is a standard 450neutral oil containing the additives and concentrations shown in Table14. Also shown in Table 14 is the result of the experiment.

                                      TABLE 14                                    __________________________________________________________________________          Compound of                                                                          Copper Corrosion                                                                              Anti- Amoco.sup.(D)                                                                       CRC L-38 Engine Test                      Example 61                                                                            Inhibitor.sup.(B)                                                                      Terephthalic                                                                         Oxidant.sup.(C)                                                                     PCO-059                                                                             40 hours                             Example                                                                            (Wt. %).sup.(A)                                                                       (Wt. %)  Acid (Wt. %)                                                                         (Wt. %)                                                                             (Wt. %)                                                                             (BWL, mg).sup.(E)                    __________________________________________________________________________    72   2.12    0.075    0.010  0.050 7.050 30.1                                 __________________________________________________________________________     .sup.(A)                                                                      1hydroxy-3,7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacycloo    tane (Example 61).                                                             .sup.(B) Copper Corrosion Inhibitor = A mixture of 83 weight percent          1,3,4thiodiazole-2,5-bis(octyldisulfide) and 17 weight percent of 2           mercapto5-octyldithio-1,3,4-thiadiazole, marketed by the Amoco Oil Compan     under the trademark of Amoco 150.                                             .sup.(C) Antioxidant = thiodiethyl bis(3,5di-t-butyl-4-hydroxy)               hydrocinnamate.                                                               .sup.(D) Amoco PCO059 = detergent/dispersant package marketed commerciall     by the Amoco Oil Company.                                                     .sup.(E) BWL = bearing weight loss.                                      

EXAMPLE 73

A lubricant composition containing 450 neutral oil,1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane, andoctyl diphenyl amine is tested for extreme pressure properties, andresistance to oxidation stability, and corrosion using a single-cylinderLabeco CLR Test Engine equipped with sintered copper (65 wt. %)/lead (35wt. %) connecting rod bearings, in accordance with the procedure ASTMSTP 509A, Part IV and the engine operating conditions of Examples 54 to60 and 72. The total phosphorus content was 0.075 weight percent.

The results are summarized in the following Table 15:

                                      TABLE 15                                    __________________________________________________________________________          E.P.  Anti- Copper                           CRC L-38 Engine Test            Additive.sup.(A)                                                                     oxidant.sup.(B)                                                                     Corrosion.sup.(C)                                                                      OLOA 267.sup.(D)                                                                      AMOCO.sup.(E)                                                                          UNAD.sup.(F)                                                                         40 hours                   Example                                                                            (wt. %)                                                                              (wt. %)                                                                             Inhibitor (wt. %)                                                                      (wt. %) PCO-059 (wt. %)                                                                        242 (wt. %)                                                                          (BWL,                      __________________________________________________________________________                                                       mg).sup.(G)                73   2.67   0.50  0.15     0.30    7.05     0.01   15.4                       __________________________________________________________________________     .sup.(A) E.P. Additive =                                                      1hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane (Example       21).                                                                          .sup.(B) Antioxidant = 4 octyldiphenyl amine.                                 .sup.(C) Copper Corrosion Inhibitor = a mixture of 83 weight percent          1,3,4thiodiazole 2,5-bis (octyldisulfide) and 17 weight percent of            2mercapto-5-octyldithio-1,3,4-thiodiazole.                                    .sup.(D) OLOA 267 = zinc dialkyl dithiaphosphate marketed commercially by     the Chevron Chemical Company.                                                 .sup.(E) AMOCO PCO059 = detergent/dispersant package marketed commerciall     by the Amoco Oil Company.                                                     .sup.(F) UNAD 242 = Siliconetype defoamant containing kerosene.               .sup.(G) BWL = bearing weight loss, e.g. a BWL of 40 mg or less is            acceptable.                                                              

EXAMPLE 74

The lubricant composition disclosed in Table 15 of Example 73 is testedin a 1977 Oldsmobile V-8 engine for 64 hours in accordance with thefollowing 1977 General Motors Lubricant Evaluation Sequence III D test.

Prior to each test run, the engine is completely disassembled, solventcleaned, measured and rebuilt in strict accordance to furnishedspecifications. Following the preparation, the engine is installed on adynamometer test stand equipped with the appropriate accessories forcontrolling speed, load, temperatures and other various engine operatingconditions.

The engine is operated on a 4-hour break-in-schedule after which oil issampled and leveled. The engine is then operated under non-cyclic,moderately high speed, high load and temperature conditions for a testduration of 64 hours, with oil leveling and oil additions each 8 hours.

In the following Table 16 is a summary of these operating conditions:

                  TABLE 16                                                        ______________________________________                                        Speed, rpm            3000 ± 20                                            Load, bhp             100 ± 2                                              (Kw)                  (74.6 ± 1.49)                                        Oil, to engine, after filter, °F.                                                            300 ± 2                                              (°C.)          (149 ± 1.1)                                          Oil pump outlet, psig min                                                                           40                                                      (atmospheres min)     (3.72)                                                  Coolant, jacket out, °F.                                                                     245 ± 1                                              (°C.)          (18.3 ± 0.6)                                         jacket in, °F. 235 ± 1                                              (°C.)          (112.8 ± 0.6)                                        jacket flow rate, gpm 60 ± 1                                               (lpm)                 (227 ± 3.8)                                          rocket cover out, °F.                                                                        240 ± 3                                              (°C.)          (115.56 ± 1.67)                                      at gpm per cover      at 1.5 ± 0.5                                         (lpm)                 (5.7 ± 1.9)                                          breather tube out, °F.                                                                       100 ± 2                                              (°C.)          (37.8 ± 1.1)                                         at gpm                at 3.0 ± 0.5                                         (1pm)                 (11.36 ± 1.9)                                        Air-fuel ratio        16.5 ± 0.5                                           Carburetor, air temperature, °F.                                                             80 ± 2                                               (°C.)          (26.7 ± 1.1)                                         Carburetor, air humidity, grains                                                                    80 ± 5                                               per lb of dry air     (0.01143 ± 0.0007)                                   (grams per gram of dry air)                                                   Carburetor, pressure, in. of water                                                                  0.1 to 0.3                                              (cm)                  (.3 to .8)                                              Blowby rate, cfm at 100° F. and 29.7 in.                                                     2.0 ± 0.3                                            (37.78° C.) and (75.4 cm) of Hg                                                              (0.0566 ± 0.0085)                                    Intake manifold vacuum, in. of Hg                                                                   7 ± 2                                                (cm)                  (17.78 ± 5.08)                                       Exhaust back pressure, in. of water                                                                 30 ± 2                                               (cm)                  (76.2 ± 5.08)                                        Exhaust back pressure, max differential,                                                            0.2 (0.51)                                              in. (cm) of water                                                             ______________________________________                                    

After every 8 hours of testing, a 25-minute shutdown period is providedfor oil sampling, additions and level adjustments. The total runningtest time for Sequence IIID is 64 hours. The results are summarized inthe following Table 17:

                  TABLE 17                                                        ______________________________________                                                                      API "SF"                                        Test                 Result   Limit                                           ______________________________________                                        (A) Engine Sludge Rating (10 = clean)                                                              9.5      9.2     min.                                    (B) Piston Varnish (10 = clean)                                                                    9.4      9.2     min.                                    (C) Cam & Lifter Wear (inch)                                                                       0.0019   0.0080  max.                                    (D) 64 hour Viscosity increase, %                                                                  182      375     max.                                    (E) Oil Consumption, quarts                                                                        3.06     6.38    max.                                    ______________________________________                                    

The engine tests are performed in accordance with the CoordinatingResearch Council (CRC) rating and techniques located in CRC Manual NOS 9and 12.

EXAMPLE 75

A sulfurized, boron-containing, heterocyclic compound is prepared bymixing 12 grams of oleylamine, 9.6 grams of styrene oxide and 200 ml oftoluene for 30 minutes at room temperature (25° C.) in a single-neckedone-liter round-bottomed flask. The flask is placed in a heating mantleand equipped with a water-cooled condenser. The mixture is heated underreflux for three hours producing an oleylamine/styrene oxide adduct.

The adduct is cooled to room temperature and 2.47 grams of boric acid isadded to the flask. Next, the resulting mixture is refluxed until 1.44ml of water collects in an added Dean-Stark trap. The flask and contentsare moved to a rotary evaporator where toluene is stripped from theboron-containing, heterocyclic compound (18 grams).

Sulfur (0.96 grams) and 75 ml of toluene are added to the round-bottomedflask and the resulting mixture is heated to reflux temperature withmixing for four hours, after which the toluene is distilled off undervacuum, to yield the desired reaction product.

EXAMPLE 76

The reaction product of Example 75 is tested for extreme pressureproperties in 450 neutral oil in accordance with the procedure disclosedin ASTM:D 32 33-73 (Reapproved 1978) using a Falex lubricant tester. Thetest is performed by applying resistance to a revolving metal journal. Arachet mechanism movably attached to two V-blocks applies resistance bysteadily increasing pressure on the journal. The metal journal andV-blocks (steel) are submerged in the lubricant composition to betested. The results are summarized in the following Table 18:

                  TABLE 18                                                        ______________________________________                                        Torque on Journal lb.-in. (Newtons-Meters)                                                              450 Neutral Oil.sup.(A)                             True Load    450 Neutral Oil.sup.(A)                                                                    with 2.25 wt. %                                     lbs. (Newtons)                                                                             without additive                                                                           additive                                            ______________________________________                                        300     (1,334)  9       (1.017)                                                                              2      (0.226)                                500     (2,224)  12      (1.356)                                                                              4      (0.452)                                750     (3,336)  xx           8      (0.904)                                  1,000   (4,448)               13     (1.469)                                  1,250   (5,560)               18     (2.034)                                  1,500   (6,672)               23     (2.599)                                  1,750   (7,784)           xx                                                  ______________________________________                                         .sup.(A) 450 Neutral Oil, marketed commercially by Union Oil Company of       California.                                                              

EXAMPLE 77

A sulfochlorinated, boron-containing, heterocyclic compound is producedby adding 20 grams of1-hydroxy-3,7-diphenyl-5-oleyl-5-aza-1-bora-2,8-dioxacyclooctane, 10 mlof toluene and 1.76 grams of sulfur monochloride to a one literround-bottomed flask equipped with heating mantle and water-cooledcondenser. The mixture thus formed is heated at 200° F. (93.33° C.) for45 minutes, then 6.3 grams of 450 neutral oil is added to the flask andthe toluene evaporated. The compound10,10'-dithiodi[9-chloro-1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl)-octadecane]is produced in this reaction.

EXAMPLE 78

The compounddithiodi-[1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl)-chlorotallow]is produced in accordance with the procedure of Example 75 with thefollowing exception:

20 grams of1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane and1.215 grams of sulfur monochloride are added to the one literround-bottomed flask.

EXAMPLES 79 TO 81

The compounds produced in Examples 77 and 78 are tested for extremepressure properties by admixing each compound with separate portions of450 neutral oil at concentrations of 2 weight percent. A sample of 450neutral oil without an additive (compound) serves as a control in theexperiment.

Each lubricant composition is tested in accordance with the proceduredisclosed in ASTM:D 32 33-73 (Reapproved 1978) using a Falex lubricanttester containing a steel journal and V-blocks. A summary of the resultsobtained disclosed in the following Table 19:

                  TABLE 19                                                        ______________________________________                                         TORQUE ON JOURNAL LB.-IN. (NEWTON-METERS)                                            Example                                                                         79       80           81                                                      450      450 Neutral Oil                                                                            450 Neutral Oil                               True Load Neutral  with 2 wt. % with 2 wt. %                                  Lbs. (Newtons)                                                                          Oil      Additive of Ex. 77                                                                         Additive of Ex. 78                            ______________________________________                                          300 (1,334)                                                                            9 (1.017)                                                                             2 (0.226)     4 (0.452)                                      500 (2,224)                                                                           14 (1.587)                                                                             3 (0.339)     6 (0.678)                                      750 (3,336)                                                                           20 (2.260)                                                                             8 (0.904)    10 (1.130)                                    1,000 (4,448)                                                                           xxx.sup.(1)                                                                            9 (1.017)    14 (1.582)                                    1,250 (5,560)      11 (1.243)   18 (2.034)                                    1,500 (6,672)      13 (1.469)   21 (2.373)                                    1,750 (7,784)      13 (1.469)   23 (2.599)                                    2,000 (8,896)      xxx          24 (2.712)                                     2,250 (10,008)                 xxx                                           ______________________________________                                         .sup.(1) xxx indicates failure occurred with the journal scoring and the      shear pin breaking.                                                      

EXAMPLE 82

A chlorinated, boron-containing, heterocyclic compound is prepared byplacing 71.3 grams of a mixture containing 75 weight percent of1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane and 25weight percent of 450 neutral oil into a 250 ml Pyrex flask equippedwith a side arm. Chlorine gas is introduced into the flask through aTygon tube attached to a glass tube equipped with a rubber stopper andextending to the bottom of the flask. The chlorine gas is bubbledthrough the heterocyclic compound with agitation. Excess gas is ventedthrough the side arm of the flask, Tygon tubing and glass tubing into anaqueous solution of 10% potassium hydroxide. The chlorine gas wasbubbled through the system for 15 minutes giving a total weight gain of3.2 grams to the heterocyclic compound. The compound thus produced is1-hydroxy-3,7-diphenyl-5-(perchlorotallow)-1-bora-2,8-dioxa-5-aza-cyclooctane.

EXAMPLE 83

A brominated, boron-containing, heterocyclic compound is prepared byplacing 71.33 grams of a mixture containing 75 weight percent of1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane and 25weight percent of 450 neutral oil into a 250 ml Pyrex flask equippedwith a heating mantle and thermometer.

Liquid bromine (6.37 grams) is added to the Pyrex flask and the mixtureis agitated for ten minutes. Next the mixture is heated at 120° F. (49°C.) for ten minutes. The compound1-hydroxy-3,7-diphenyl-5-(perbromotallow)-1-bora-2,8-dioxa-5-aza-cyclooctane is produced.

EXAMPLE 84 TO 88

The compounds produced in Examples 82 and 83 are tested for extremepressure properties by admixing each compound with separate portions ofSAE 30 motor oil containing 0.05 weight percent phosphorus (added aszinc dialkyldithiophosphate) and the concentration of additive indicatedin Table 20 below. A sample of the control SAE 30 motor oil (Example 47)without an additive (borate of the present invention) serves as acontrol in the experiment.

Each lubricant composition is tested in accordance with the proceduredisclosed in ASTM:D 32 33-73 (Reapproved 1978) using a Falex lubricanttester containing a steel journal and V-blocks. A summary of resultsobtained is disclosed in the following Table 20:

                                      TABLE 20                                    __________________________________________________________________________    TORQUE ON JOURNAL LB.-IN. (NEWTON-METERS)                                            Example                                                                       84     85       86       87       88                                          (SAE 30 Oil)                                                                         Oil with Additive                                                                      Oil with Additive                                                                      Oil with Additive                                                                      Oil with Additive                    True Load                                                                            Control                                                                              of       of       of       of                                   lbs. (Newtons)                                                                       47     Ex. 83 (1 wt. %)                                                                       Ex. 82 (1 wt. %)                                                                       Ex. 82 (2 wt. %)                                                                       Ex. 82 (5 wt. %)                     __________________________________________________________________________      300 (1,334)                                                                        13 (1.469)                                                                            9 (1.017)                                                                              9 (1.017)                                                                              8 (0.904)                                                                              6 (0.678)                             500 (2,224)                                                                        16 (1.808)                                                                           15 (1.695)                                                                             13 (1.469)                                                                             11 (1.243)                                                                              8 (0.904)                             750 (3,336)                                                                        30 (3.389)                                                                           22 (2.486)                                                                             20 (2.260)                                                                             20 (2.260)                                                                             12 (1.356)                             755 (3,358)                                                                        Shear  --       --       --       --                                     950 (4,226)                                                                        --     Shear    --       --       --                                   1,000 (4,448)                                                                        --     --       25 (2.825)                                                                             24 (2.712)                                                                             16 (1.808)                           1,100 (4,893)                                                                        --     --       Shear    --       --                                   1,250 (5,560)                                                                        --     --       --       30 (3.389)                                                                             19 (2.147)                           1,300 (5,782)                                                                        --     --       --       Shear    --                                   1,450 (6,450)                                                                        --     --       --       --       Shear                                __________________________________________________________________________     The above data indicate that the boroncontaining heterocyclic compounds       described above impart extreme pressure lubricating properties to SAE 30      motor oil at the indicated concentrations.                               

EXAMPLE 89

Tests were conducted to determine the effects on water stability ofvarious boron-containing compounds of formula (I) hereinbefore whereinR₁ and R₂ were unsubstituted ethylene groups, M was hydrogen, and Rcontained between 8 and 20 carbon atoms and was either an alkyl group oran alkenyl group with only one double bond in the chain. The same testswere also conducted to determine the water stability of variousboron-containing compounds of formula (II) hereinbefore wherein R₄, R₇,R₈, R₉, R₁₀, R₁₁, and M were hydrogen, R₅ and R₆ were unsubstitutedphenyl radicals (i.e., a benzene ring), and R₃ varied as R in formula(I) discussed above.

The purpose of the experiment was to determine if, in the presence ofwater, said boron compounds would form an emulsion. All lubricating oilscontain water (or come into contact with water) to some extent, and tothe degree that the boron compound resists forming an emulsion inoil-water mixtures, to that same extent is it a more desirable additivefor engine lubricating oils.

The tests were conducted as follows:

Into a test tube was placed sufficient water and lubricating oilcontaining the boron compound to be tested so that the water and oileach formed about 50 percent of the contents of the test tube. Thecontents were then shaken vigorously, after which the test tube wasvisually inspected to see if an emulsion had formed (indicative of waterinstability) or if two separate, clearly defined phases settled out(indicative of water stability).

Upon visual inspection of the various samples, it was found that theboron compound of formula (II) consistently produced a clearly defined,two-phase liquid indicative of a boron additive stable to water in alubricating environment. In contrast, the formula (I) compoundconsistently formed an emulsion indicative of instability in thepresence of water in a lubricating environment.

In yet other tests, it was found that the formula (II) compounds wereless corrosive to lead and copper bearings in automotive engines and thelike than the above-described formula (I) compounds.

From these tests, and the data shown in previous examples, the followingwas concluded: although the formula (I) compound is a highly usefullubricating oil additive, particularly in situations wherein the waterconcentration of the oil can be minimized, the formula (II) compoundpossessed unexpectedly superior properties thereto with respect to waterstability and corrosion inhibition.

EXAMPLE 90

The boron-containing heterocyclic compounds listed in Table 21 belowwere tested for oil solubility by adding 2 grams of each compound andseparate samples of 98 grams of 450 neutral oil to 250 ml Pyrex beakersequipped with teflon-coated, magnetic stirring bars which had lengths of11/2 inches and diameter of 1/4 inch. The Pyrex beakers were placed onModel PC-351 Corning hot plates and the boron-containing heterocycliccompound-450 neutral oil mixtures were heated at temperatures of 120° F.with stirring (400 RPM of stirring bars) for ten minutes.

The Pyrex beakers were removed from the hot plates and theboron-containing heterocyclic compound-450 neutral oil mixtures wereexamined for oil solubility of said compound in each sample. The resultsare summarized in the following Table 21:

                                      TABLE 21                                    __________________________________________________________________________    Oil Solubility Chart                                                           ##STR17##                                                                    General Formula                                                               Compound Name             R          R.sub.1 and R.sub.2                                                                    Solubility                      __________________________________________________________________________    1. Methylamine di(ethylate)hydrogen borate                                                              Methyl(C.sub.1)                                                                          C.sub.2 Carbon Chain                                                                   Insoluble                       2. Octylamine di(ethylate)hydrogen borate                                                               Octyl(C.sub.8)                                                                           C.sub.2 Carbon Chain                                                                   Insoluble                       3. Octylamine di(-2-methylethylate)hydrogen borate                                                      Octyl(C.sub.8)                                                                           C.sub.3 Carbon Chain                                                                   Insoluble                       4. Octylamine di(-2-ethylethylate)hydrogen borate                                                       Octyl(C.sub.8)                                                                           C.sub.4 Carbon Chain                                                                   Insoluble                       5. Dodecylamine di(-2-methylethylate)hydrogen borate                                                    Dodecyl(C.sub.12)                                                                        C.sub.3 Carbon Chain                                                                   Soluble                         6. Dodecylamine di(-2-ethylethylate)hydrogen borate                                                     Dodecyl(C.sub.12)                                                                        C.sub.4 Carbon Chain                                                                   Soluble                         7. Cocoamine di(-2-ethylethylate)hydrogen borate                                                        Coco(C.sub.12 average)                                                                   C.sub.4 Carbon Chain                                                                   Soluble                         8. Octadecyl di(-2-methylethylate)hydrogen borate                                                       Octadecyl(C.sub.18)                                                                      C.sub.3 Carbon Chain                                                                   Soluble                         9. Tallow di(-2-methylethylate)hydrogen borate                                                          Tallow(C.sub.18 average)                                                                 C.sub.3 Carbon Chain                                                                   Soluble                         __________________________________________________________________________

The data in Table 21 show that boron-containing heterocyclic compoundsare not soluble in 450 neutral oil at concentrations of 2 weight percentwhen the R group attached to the nitrogen atom of said compoundscontains 8 or less carbon atoms. In contrast, boron-containingheterocyclic compounds are soluble in 450 neutral oil at concentrationsof 2 weight percent when the R group contains 12 or more carbon atoms.

Based on these data, it is concluded that the oil solubility of theboron-containing heterocyclic compounds is directly related to thelength of the carbon chain in the R group attached to the nitrogen atomof the amine moiety in said boron-containing heterocyclic compound, andthat boron-containing heterocyclic compounds with 9 or more carbon atomsin the R group attached to the nitrogen atom of the amine moiety of saidcompounds are more soluble in oil than when said R group contains 8 orless carbon atoms.

Several other factors should also be considered when assessing the datain Table 21. One such is that the data are indicative of solubilities ina specific oil, i.e., a 450 neutral oil, and that for other oils, e.g.,silicone synthetic oils, some of the boron compounds shown as insolublemay prove soluble. Thus, the data indicate the relative solubility ofone boron compound versus another, not the absolute solubility of boroncompounds in all oils. Another factor to be considered is the effect ofthe length of the R₁ and R₂ groups. The data clearly indicate, whenthese groups contain only about 4 carbon atoms or less, that thesolubility of the compound will be a function of the length of the Rcarbon chain. However, one can also increase the solubility of the boroncompounds by altering the R₁ and R₂ groups. For example, compounds offormulae (II) and (III) hereinbefore are soluble in 450 neutral oil,even when the R group side chain is relatively small. As anillustration, it is now known that a compound falling within formula(II), i.e.,1-hydroxy-3,7-diphenyl-5-butyl-5-aza-1-bora-2,8-dioxacyclooctane, isknown to be readily soluble in 450 neutral oil, despite the fact thatthe R group side chain is a relatively small butyl group. Thus, therelative solubility of boron compounds herein are dependent on both thelength of the R group side chain and the length and nature of the R₁ andR₂ groups.

EXAMPLE 91

This Example compares the solubility and extreme pressure properties ofboron compounds of the invention versus those disclosed in U.S. Pat. No.3,227,739.

The procedure described in Example 1 of U.S. Pat. No. 3,227,739 wasfollowed to prepare N,N-diethanol 2-hydroxy C₁₆ -C₁₈ amine with thefollowing exception:

Since the FMC Corporation no longer commercially produces the C₁₆ -C₁₈epoxide used, 1,2 epoxyoctadecane was substituted for the FMC epoxide.The reaction produced N,N-diethanol, 2-hydroxy C₁₈ amine.

The procedure described in Example 2 of U.S. Pat. No. 3,227,739 wasfollowed to prepare the boric acid adduct of N,N-diethanol, 2-hydroxyC₁₈ amine. The product thus produced (Compound A) was solid at roomtemperature.

Test No. 1

The boric acid adduct of N,N-diethanol, 2-hydroxy C₁₈ amine and thetallowaminodiethylate hydrogen borate (Compound B) produced in Example 2hereinbefore were tested for oil solubility by adding the weightpercentages indicated in Table 22 below to 450 neutral oil. Thedesignated samples, including 450 neutral oil (100 grams total), wereadded to 250 ml Pyrex beakers equipped with teflon-coated, magneticstirring bars which had lengths of 21/2 inches and diameters of 1/4inch. The Pyrex beakers were placed on Model PC-351 Corning hot platesand heated to the temperatures indicated in Table 22 with stirring (400RPM of stirring bars) for ten minutes.

The Pyrex beakers were removed from the hot plates, and the 450 neutraloil mixtures were examined for oil solubility of the respectivecompounds in each sample. The results are summarized in the followingTable 22:

                                      TABLE 22                                    __________________________________________________________________________    OIL SOLUBILITY CHART (450 Neutral Oil)                                                                              SOLUBILITY AT 77° F.             COMPOUND CONCENTRATION (wt. %)                                                                        TEMPERATURE °F. (°C.)                                                         (25° C.)                         __________________________________________________________________________    1. Compound A*                                                                         0.5            260° F. (126.67° C.)                                                          Cloudy, sediment                        2. Compound A                                                                          1.0            260° F. (126.67° C.)                                                          Cloudy, sediment                        3. Compound A                                                                          2.0            260° F. (126.67° C.)                                                          Cloudy, semi-gel                        4. Compound B**                                                                        0.5            130° F. (54.44° C.)                                                           Clear, soluble                          5. Compound B                                                                          1.0            130° F. (54.44° C.)                                                           Clear, soluble                          6. Compound B                                                                          2.0            130° F. (54.44° C.)                                                           Clear, soluble                          __________________________________________________________________________     *Boric acid adduct of N,N--diethanol, 2hydroxy C.sub.18 amine prepared        according to Examples 1 and 2 of U.S. Pat. No. 3,227,739.                     **Tallowaminodiethylate hydrogen borate, where tallow = C.sub.18 average.

Several temperatures were used in an attempt to fully dissolve CompoundA, i.e., the boric acid adduct of N,N-diethanol, 2-hydroxyamine, in 450neutral oil. At temperatures of 130° F. (54.44° C.), 200° F. (93.33° C.)and 225° F. (107.22° C.), the compound was insoluble in 450 neutral oil.The compound was soluble in 450 neutral oil at 260° F. (126.67° C.);however, upon cooling a cloudy appearance and sediment in the oil wasnoted. A concentration of 2 weight percent of Compound A produced a veryviscous, semi-gel when mixed with 450 neutral oil and was unacceptableas an additive for the oil at this concentration.

Compound B, i.e., tallowaminediethylate hydrogen borate, was fullysoluble in all samples tested at the standard 130° F. (54.44° C.) mixingtemperature for oil additives and did not precipitate from the oil uponstanding and cooling.

TEST NO. 2

The boric acid adduct of N,N-diethanol, 2-hydroxy C₁₈ amine and thetallowaminodiethylate hydrogen borate were also tested for oilsolubility in the low phosphorus control SAE 30 motor oil (Example 47)in accordance with the procedure described above. The results aresummarized in the following Table 23:

                                      TABLE 23                                    __________________________________________________________________________    OIL SOLUBILITY IN SAE 30 MOTOR OIL (EXAMPLE 47)                                                                     SOLUBILITY AT 77° F.             COMPOUND CONCENTRATION (wt %)                                                                         TEMPERATURE °F. (°C.)                                                         (25° C.)                         __________________________________________________________________________    1. Compound A*                                                                         0.5            260° F. (126.67° C.)                                                          Hazy, slight sediment                   2. Compound A                                                                          1.0            260° F. (126.67° C.)                                                          Hazy, moderate sediment                 3. Compound A                                                                          2.0            260° F. (126.67° C.)                                                          Hazy, heavy sediment                    4. Compound B**                                                                        0.5            130° F. (54.44° C.)                                                           Clear, soluble                          5. Compound B                                                                          1.0            130° F. (54.44° C.)                                                           Clear, soluble                          6. Compound B                                                                          2.0            130° F. (54.44° C.)                                                           Clear, soluble                          __________________________________________________________________________     *Boric acid adduct of N,N-diethanol, 2hydroxy C.sub.18 amine prepared         according to Examples 1 and 2 of U.S. Pat. No. 3,227,739.                     **Tallowaminodiethylate hydrogen borate, where tallow = C.sub.18 average.

As shown in Table 23, Compound A was insoluble in the SAE 30 motor oilat all concentrations tested at temperatures of 130° F. (54.44° C.),200° F. (93.33° C.) and 225° F. (107.22° C.). At a temperature of 260°F. (126.67° C.), the compound did dissolve in the SAE 30 motor oil;however, upon standing, a sediment was noted in each sample.

By comparison, Compound B was soluble in the SAE 30 motor oil in allsamples tested at a temperature of 130° F. (54.44° C.). The compoundremained in solution and did not form a precipitate or sediment in theoil upon standing.

TEST NO. 3

The boric acid adduct of N,N-diethanol, 2-hydroxy C₁₈ amine andtallowaminodiethylate hydrogen borate, both described above, were testedfor extreme pressure properties in accordance with the proceduredisclosed in ASTM:D 3233-73 (Reapproved 1978) using a Falex lubricanttester. The test, in accordance with the above ASTM designation, wasperformed by applying resistance (torque) to a revolving metal journal.A rachet mechanism movably attached to two V-blocks applied resistanceby steadily increasing pressure on the journal. The metal journal andV-blocks, both constructed of steel, were submerged in the lubricantcomposition to be tested. The base oil in the experiments was thecontrol SAE 30 motor oil (Example 47). The SAE 30 motor oil was chosenas the base oil because the boric acid adduct of N,N-diethanol,2-hydroxy C₁₈ amine was slightly more soluble in this oil and did notproduce a semi-gel at higher concentrations as compared to 450 neutraloil. However, this compound was not tested in the Falex lubricant testerat a concentration of 2 weight percent because at this concentrationsevere solubility problems were encountered in both the 450 neutral oiland the SAE 30 motor oil. The results are summarized in the followingTable 24:

                                      TABLE 24                                    __________________________________________________________________________    TORQUE ON JOURNAL LBS.-IN. (NEWTON METERS)                                    True    SAE 30  SAE 30  SAE 30  SAE 30                                        Load    with 0.5 wt. %                                                                        with 1.0 wt. %                                                                        with 0.5 wt. %                                                                        with 1.0 wt. %                                lbs. (Newtons)                                                                        Compound A*                                                                           Compound A*                                                                           Compound B**                                                                          Compound B**                                  __________________________________________________________________________      300 (1,334)                                                                         12 (1.356)                                                                            12 (1.356)                                                                             9 (1.017)                                                                            10 (1.130)                                      500 (2,224)                                                                         20 (2.260)                                                                            15 (1.695)                                                                            12 (1.356)                                                                            11 (1.243)                                      700 (3,114)                                                                         Journal --      --      --                                                    Shear                                                                   750 (3,336)   20 (2.260)                                                                            16 (1.808)                                                                            14 (1.582)                                      925 (4,114)   --      --      --                                            1,000 (4,448)   33 (3.729)                                                                            20 (2.260)                                                                            16 (1.808)                                    1,050 (4,670)   Journal --      --                                                            Shear                                                         1,250 (5,560)           24 (2.712)                                                                            20 (2.260)                                    1,350 (6,005)           Journal --                                                                    Shear                                                 1,450 (6,450)                   Journal                                                                       Shear                                         __________________________________________________________________________     *Boric acid adduct of N,N--diethanol, 2diethanol, 2hydroxy C.sub.18 amine     **Tallowaminodiethylate hydrogen borate.                                 

As shown in the foregoing Table 24, the compound prepared in accordancewith the procedure of U.S. Pat. No. 3,227,739 had inferior extremepressure properties when compared with Compound B prepared according tothe procedure of Example 2 hereinbefore. In contrast, the data in Table24 show that tallowaminodiethylate hydrogen borate exhibits superiorextreme pressure properties when added to SAE 30 motor oil as comparedto the boric acid adduct of N,N-diethanol, 2-hydroxy C₁₈ amine. Andbased on the data in Tables 22 and 23 above, compounds of the typedisclosed in U.S. Pat. No. 3,227,739 experience oil solubility problemsin 450 neutral oil and SAE 30 motor oil at concentrations of 0.5, 1.0,and 2.0 weight percent. In contrast, the tallowaminodiethylate hydrogenborate is completely soluble at such concentrations.

EXAMPLE 92

This example compares the solubility and extreme pressure properties ofa compound disclosed in U.S. Pat. No. 3,224,971 against the boroncompounds produced according to Examples 1 and 2 hereinbefore.

The tris (borate ester) of bis (o-hydroxy-octylphenylmethyl) amine wasprepared in accordance with the procedure in Example 3 (column 3, lines39 to 69) of U.S. Pat. No. 3,224,971.

The borate ester was prepared by mixing 205 grams of 5-octylphenol, 23.4grams of hexamethylenetetramine and 500 ml of toluene in a single-neckedone-liter round-bottomed flask. The flask was placed in a heating mantleand fitted with a Dean-Stark trap and water-cooled condenser. Themixture was refluxed for 24 hours. Next, 20.6 grams of boric acid wereadded to the flask and the mixture was refluxed for an additional fourhours during which water produced in the reaction was collected in theDean-Stark trap.

Test No. 1

An experiment was performed to compare the boron compounds of Examples 1and 2 hereinbefore with the borate ester described above in the RyderGear Test disclosed in column 6, lines 1 to 48 and Table 6 of U.S. Pat.No. 3,224,971. The base oil used in the test was di-2-ethyl-hexylsebacate.

A one-gram sample of the boron compound of Example 1 hereinbefore wasadmixed with 99 grams of di-2-ethyl-hexyl sebacate at 120° F. (48.89°C.) in a 250-ml Pyrex glass beaker. The boron compound did not dissolvein the base oil. The mixture formed was cloudy and the boron compoundsettled to the bottom of the beaker upon standing. The mixture washeated to 300° F. (148.89° C.); however, the boron compound did notdissolve in the di-2-ethyl-hexyl sebacate.

Next, a one-gram sample of the boron compound of Example 2 hereinbeforewas admixed with 99 grams of di-2-ethyl-hexyl sebacate at 120° F.(48.89° C.) in a 200-ml Pyrex glass beaker. This boron compound did notdissolve in the base oil. The base oil and boron compound mixture washeated to 300° F. (148.89° C.), but the boron compound still did notdissolve in the base oil.

Additional experiments to determine the effectiveness of the two boroncompounds as extreme pressure agents in the Ryder Gear Test were notconducted, because the compounds would not go into solution in thedi-2-ethylhexyl sebacate base oil. However, experiments were conductedto compare the effectiveness in an SAE 10W 40 motor oil of thesecompounds and the tris borate esters of U.S. Pat. No. 3,224,971 asextreme pressure agents in a Falex lubricant tester.

Test No. 2

The boron compounds of Examples 1 and 2 and the tris (borate ester) ofbis (o-hydroxy-octylphenylmethyl) amine described above were tested inaccordance with the procedure disclosed in ASTM D3233-73 (Reapproved1978) using a Falex lubricant tester. The test was performed by applyingresistance to a revolving metal journal. A rachet mechanism movablyattached to two V-blocks applied resistance by steadily increasingpressure on the journal. The metal journal and V-blocks, bothconstructed of steel, were submerged in the lubricant composition to betested. The base oil in the experiments was an SAE 10W/40 motor oilmarketed commercially by the Union Oil Company of California. Theresults are summarized in the following Table 25:

                  TABLE 25                                                        ______________________________________                                                               Highest Jaw Load                                                              Before Failure,                                        Composition            Lbs. (Newtons)                                         ______________________________________                                        (1)  SAE 10W/40 oil without any                                                                          1,400   (6,227)                                         additive                                                                 (2)  SAE 10W/40 oil plus 1.0 wt. %                                                                       1,700   (7,562)                                         Example 1 compound                                                       (3)  SAE 10W/40 oil plus 1.0 wt. %                                                                       2,250   (10,008)                                        Example 2 compound                                                       (4)  SAE 10W/40 oil plus 1.0 wt. %                                                                       900     (4,003)                                         tris borate ester of bis (o-                                                  hydroxy-octylphenylmethyl) amine                                         (5)  SAE 10W/40 oil plus 2.0 wt. %                                                                       900     (4,003)                                         tris borate ester of bis (o-                                                  hydroxy-octylphenylmethyl) amine                                         ______________________________________                                    

As shown in Table 25 above, the Example 1 and 2 compounds substantiallyincreased the load carrying property (extreme pressure property) of SAE10W/40 base oil in the Falex lubricant tester, while bis(o-hydroxyoctylphenylmethyl) amine had a detrimental effect upon thebase oil, reducing the load carrying property of said oil by 500 pounds.The amount of bis (o-hydroxy-octylphenylmethyl) amine added to the baseoil was doubled with the same detrimental effect noted.

Test No. 3

The boron compound of Example 1 hereinbefore and the tris (borate ester)of bis (o-hydroxy-octylphenylmethyl) amine described above were testedin accordance with the procedure of Test No. 2 with the followingexception: 450 neutral oil marketed by the Union Oil Company ofCalifornia was substituted for the SAE 10W/40 oil. The results aresummarized in the following Table 26:

                  TABLE 26                                                        ______________________________________                                                               Highest Jaw Load                                                              Before Failure,                                        Composition            Lbs. (Newtons)                                         ______________________________________                                        (1)  450 neutral without additive                                                                        700     (3,114)                                    (2)  450 neutral oil plus 1.0 wt. %                                                                      1,100   (4,893)                                         Example 1 compound                                                       (3)  450 neutral oil plus 1.0 wt. %                                                                      700     (3,114)                                         tris borate ester of bis (o-                                                  hydroxy-octylphenylmethyl) amine                                         (4)  450 neutral oil plus 5.0 wt. %                                                                      700     (3,114)                                         tris borate ester of bis (o-                                                  hydroxy-octylphenylmethyl) amine                                         ______________________________________                                    

As shown in Table 26 above, the boron compound of Example 1 increasedthe load carrying property (extreme pressure) of 450 neutral base oil inthe Falex lubricant tester. Bis (o-hydroxyoctylphenylmethyl) amine didnot affect the base oil either positively or negatively; theload-carrying property of the base oil was the same with or without theadditive.

EXAMPLE 93

The combination of a solution of an oil-soluble copper carboxylate suchas copper naphthenate and a boron-containing heterocyclic compound bothsulfurized and nonsulfurized gives better anti-wear protection in an oilthan either component separately.

In the four-ball wear test (40 kg., 600 rpm, 167° F. (75° C.), 1 hour(ASTM D 4172-82 modified to run at 600 rpm)), one loaded steel ballrotates against three stationary balls. The average wear scar diameterof the three stationary balls is a measure of wear. The reported wearscar diameters are the average scar diameters minus the Hertz scardiameter (the average diameter in millimeters of an indentation causedby the deformation of the balls under static load, calculated from D_(h)=8.73×10⁻² (P)^(1/3) where D_(h) is the Hertz diameter of the contactarea, and P is the static applied load).

The four-ball wear scar test was performed on an automotive oil (450neutral) containing the ingredients indicated in Table 27, with theresults of the tests also being indicated therein. The borates of theinvention all give better wear protection than copper naphthenate.However, a combination of copper naphthenate solution and boratessolution gives significantly better wear protection than eithercomponent alone. Therefore, there is a synergistic interaction betweencopper naphthenate and the borates of the invention.

                  TABLE 27                                                        ______________________________________                                        EFFECT OF COPPER PLUS BORATES ON                                              ANTI-WEAR PERFORMANCE                                                         Cu       Borate    Borate    Borate   Scara Dia-                              Naphthenate                                                                            (I).sup.1 conc.,                                                                        (II).sup.2 conc.,                                                                       (III).sup.3 conc.,                                                                     meter,                                  conc., wt. %                                                                           wt. %     wt. %     wt. %    mm.sup.4                                ______________________________________                                        2.0      --        --        --       0.22                                    --       1.5       --        --       0.18                                    --       --        2.0       --       0.15                                    --       --        --        2.0      0.18                                    1.0      0.75      --        --       0.10                                    1.0      --        1.0       --       0.12                                    1.0      --        --        1.0      0.06                                    ______________________________________                                         .sup.1 Borate (I) is a sulfurized                                             1hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.             .sup.2 Borate (II) is                                                         1(2,6-di-tert-butyl-4-methylphenoxy)-3,7-dimethyl-5-tallow-5-aza-1-bora-2    8-dioxacyclooctane.                                                            .sup.3 Borate (III) is a sulfurized Borate (II).                              .sup.4 Average scar diameter minus Hertz scar diameter.                  

EXAMPLE 94

Tallowamine (distilled) from Armak Chemical Company (94.04 grams, 0.35mole), styrene oxide from Union Carbide (94.21 grams, 0.70 moles) andtoluene (200 ml) were stirred at room temperature for 30 minutes in around-bottomed flask equipped with a reflux condenser. The mixture(solution) was heated to the reflux temperature of toluene for threehours producing an amine:styrene oxide adduct. The adduct was cooled inthe flask to room temperature (25° to 30° C.) and boric acid (21.75gram, 0.35 mole) was added. A Dean Stark-type water separation apparatuswas inserted between the flask and condenser. After 12.5 ml of water wascollected in the Dean Stark sidearm, the reaction was presumed to beover. The flask and contents were then moved to a rotary evaporator tostrip off the toluene leaving the product,1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane. Thisborate of the invention (75 g) and 100 ml of toluene are refluxed in around-bottomed flask. 2.2 g of sulfur is added to the refluxing mixture.The solution continued to reflux for 4 hours, then cooled to roomtemperature where 25 g of 450 neutral oil is added and the toluene iseliminated by rotary evaporation. The product is a brown, viscous stickyoil, i.e., a sulfurized form of1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.

This patent application incorporates by reference the following U.S.patents and patent applications in their entireties: U.S. Pat. No.4,400,284, U.S. Pat. No. 4,410,436, U.S. Pat. No. 4,412,928, U.S. Pat.No. 4,427,560, U.S. Pat. No. 4,490,265, U.S. patent application Ser. No.158,981 filed June 12, 1980, U.S. patent application Ser. No. 329,385filed Dec. 10, 1981, U.S. patent application Ser. No. 418,196 filedSept. 15, 1982, U.S. patent application Ser. No. 476,513 filed Mar. 18,1983, U.S. patent application Ser. No. 525,691 filed Aug. 23, 1983, U.S.patent application Ser. No. 525,718 filed Aug. 23, 1983, U.S. patentapplication Ser. No. 525,719 filed Aug. 23, 1983, U.S. patentapplication Ser. No. 525,720 filed Aug. 23, 1983, and U.S. patentapplication Ser. No. 679,286 filed Dec. 7, 1984.

Obviously, many modifications and variations of this invention, ashereinbefore set forth, may be made without departing from the spiritand scope thereof. For example, although the specification focused onthe preferred embodiment relating to oils for use in gasolinepoweredautomotive engines, the borates of the invention are useful inlubricating oils for diesel engines. In fact, it has been discoveredthat the borates of the invention, and especially the sulfurized versionof 1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane,the most preferred borate of the present invention, markedly reduceand/or prevent the formation of deposits in the upper ring zone ofdiesel engines, such as the Caterpillar 1-H2 Diesel Engine. Thus, it isintended that this embodiment of the invention and other suchmodifications and variations falling within the spirit and scope of theappended claims are embraced within the present invention.

We claim:
 1. A composition comprising:(A) a major amount of alubricating oil; (B) a minor amount of a boron-containing heterocycliccompound of the formula: ##STR18## wherein: y is an integer;M is ametal, metalloid, semi-metal, or organic or radical; R is an organic orinorganic radical; and R₁ and R₂ are the same or different organicradical; (C) a minor amount of a compound of the formula ##STR19##wherein R₄₆ and R₄₇ are moieties selected from hydrogen or straight orbranched chain alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkylradicals having from 2 to about 30 carbon atoms, provided that R₄₆ andR₄₇ are not both hydrogen and w and z are numbers from 1 to about 8; (D)a minor amount of terephthalic acid; and (E) a minor amount of acompound of the formula: ##STR20## wherein R₄₈ and R₄₉ are the same ordifferent alkyl radical having from 1 to 6 carbon atoms.
 2. Thecomposition of claim 1 wherein R₁ and R₂ are the same or differentradical of the formula: ##STR21## wherein R₃, R₄, R₅ and R₆ are the sameor different organic radical, provided that at least one is an aryl,arylalkyl or alkylaryl radical.
 3. The composition of claim 2 whereinthe aryl, arylalkyl, or alkylaryl radical is bonded to the carbonadjacent the oxygen.
 4. The composition of claim 1 wherein R₁ and R₂ arethe same or different radical ##STR22## wherein R₁₇ is a C₁ to C₅₀organic radical, provided that the carbon to which the ether group isbonded is further bonded to the oxygen of the boron-containing compound.5. The composition of claim 3 wherein the boron-containing heterocycliccompound is from about 0.1 to about 15 weight percent of thecomposition.
 6. The composition of claim 3 or 4 wherein theboron-containing heterocyclic compound is from 0.5 to 10 weight percentof the composition.
 7. The composition of claim 3 wherein M is a metal.8. The composition of claim 3 wherein M is a transition metal having anatomic number of 21 through 30 or a Group IVA metal.
 9. The compositionof claim 3 wherein M is copper.
 10. The composition of claim 3 wherein Mis a C₁ to C₅₀ organic radical.
 11. The composition of claim 3 wherein Mis derived from an aliphatic, alicyclic, or aromatic compound.
 12. Thecomposition of claim 3 wherein M is a substituted or unsubstitutedalkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radical.
 13. Thecomposition of claim 3 wherein M is a methyl or cyclohexyl radical. 14.The composition of claim 5, 7, 9, or 11 wherein R is a C₁ to C₃₀ organicradical.
 15. The composition of claim 12 wherein R is a C₁ to C₃₀organic radical.
 16. The composition of claim 13 wherein R is a C₁ toC₂₀ organic radical.
 17. The composition of claim 14 wherein R isderived from an aliphatic, alicyclic, or aromatic compound.
 18. Thecomposition of claim 12 wherein R is derived from an aliphatic compoundcontaining at least 7 carbon atoms.
 19. The composition of claim 12wherein R is derived from an aromatic compound containing at least 9carbon atoms.
 20. The composition of claim 12 wherein R is a substitutedor unsubstituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkylradical.
 21. The composition of claim 13 wherein R is a substituted orunsubstituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkylradical.